Explosive emulsion

ABSTRACT

Emulsifiers are disclosed which comprise the reaction product of component (I) with component (II). Component (I) comprises the reaction product of certain carboxylic acids or anhydrides, or ester or amide derivatives thereof, with ammonia, at least one amine, at least one alkali and/or at least one alkaline-earth metal. Component (II) comprises certain phosphorous-containing acids; or metal salts of said phosphorous-containing acids, the metals being selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver zinc, cadmium, aluminum, tin, lead, and mixtures of two or more thereof. These emulsifiers are useful in water-in-oil explosive emulsions.

This application is a continuation-in-part of U.S. Ser. No. 367,185,filed June 16, 1989, which was a continuation of U.S. Ser. No. 931,377,filed Nov. 14, 1986. This application is also a continuation-in-part ofU.S. Ser. No. 137,303, filed Dec. 23, 1987. This application is also acontinuation-in-part of U.S. Ser. No. 265,877, filed Nov. 1, 1988, whichwas a division of U.S. Ser. No. 137,301, filed Dec. 23, 1987 (now U.S.Pat. No. 4,828,633). These prior applications are incorporated herein byreference in their entireties.

TECHNICAL FIELD

This invention relates to novel compositions that have utility asemulsifiers, and to explosive emulsions containing these compositions.More particularly, this invention relates to compositions comprising thereaction product of component (I) with component (II), component (I)comprising certain carboxylic acids or anhydrides, or esters or amidesderived therefrom, reacted with ammonia, at least one amine, at leastone alkali metal and/or at least one alkaline-earth metal, component(II) comprising certain phosphorus-containing acids, or metal salts ofsaid phosphorus-containing acids, the metals being selected from thegroup consisting of magnesium, calcium, strontium, chromium, manganese,iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium,aluminum, tin, lead, and mixtures of two or more thereof. Thesecompositions are useful as emulsifiers in water-in-oil explosiveemulsions.

BACKGROUND OF THE INVENTION

The prior art discloses a large number of dispersants for use in fuelsand lubricants which are derivatives of carboxylic acid acylatingagents. Typically, the acylating agents are prepared by the reaction ofan olefin (e.g., a polyalkylene such as polyisobutylene) or a derivativethereof, containing for example at least about 10 aliphatic carbon atomsand generally at least about 30 or at least about 50 aliphatic carbonatoms, with an unsaturated carboxylic acid or derivative thereof such asacrylic acid, methylacrylate, maleic acid, fumaric acid or maleicanhydride. Dispersants are prepared from the carboxylic acid acylatingagents by reaction with, for example, amines characterized by thepresence within their structure of at least one N-H group, alcohols,reactive metal or reactive metal compounds, and combinations of theabove. The prior art relative to the preparation of such carboxylic acidderivatives is summarized in U.S. Pat. No. 4,234,435.

It also has been suggested that carboxylic acid derivative compositionssuch as those described above can be post-treated with various reagentsto modify and improve the properties of the compositions. Acylatednitrogen compositions prepared by reacting the acylating agentsdescribed above with an amine can be post-treated, for example, bycontacting the acylated nitrogen compositions thus formed with one ormore post-treating reagents such as phosphoric acid, boron oxide, boronoxide hydrate, boron halides, boron acids, esters of boron acid, carbondisulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acidacylating agents, aldehydes, ketones, epoxides, etc. Lists of the priorart relating to post-treatment of carboxylic ester and amine dispersantswith reagents such as those described above are contained in a varietyof patents such as U.S. Pat. No. 4,203,855 (Col. 19, lines 16-24) andU.S. Pat. No. 4,234,435 (Col. 42, lines 33-46).

U.S. Pat. No. 4,234,435 describes lubricating oils containing carboxylicacid derivative compositions prepared by post-treating acylated amineswith a variety of post-treating reagents including hydrocarbylthiophosphates and hydrocarbyl thiophosphites (Col. 41, lines 67-68).

The use of metal salts, expecially zinc salts, of phosphorodithioicacids as extreme pressure (E.P.) agents, corrosion inhibitors andantioxidants in lubricants is disclosed, for example, in U.S. Pat. Nos.3,390,082; 4,263,150; 4,282,171; 4,289,635; 4,308,154; 4,320,019;4,357,250; 4,417,990; and 4,446,039.

U.S. Pat. Nos. 4,329,249; 4,368,133; 4,435,297; 4,447,348; 4,448,703;and 4,666,620 disclose the use of nitrogen-containing carboxylicdispersants in water based functional fluids. These dispersants are madeby reacting a carboxylic acid acylating agent having at least onehydrocarbyl substituent of from about 12 to about 500 carbon atoms withat least one N-(hydroxyl-substituted hydrocarbyl) amine,hydroxyl-substituted poly(hydrocarbyloxy) analog of said amine, ormixtures thereof. These patents indicate that preferred acylating agentsinclude the substituted succinic acids or anhydrides, such aspolyisobutenyl-substituted succinic anhydride, and the amines that areuseful include the primary, secondary and tertiary alkanol amines, suchas diethylethanolamine. The nitrogen-containing dispersants are usefulin dispersing oil-soluble, water-insoluble functional additives inwater-based functional fluids. Among the functional additives that canbe dispersed is zinc salt of O,O'-di(isooctyl)phosphorodithioic acid.

U.S. Pat. No. 4,772,739 discloses nitrogen- and phosphorus-containingcompositions which are useful as E.P., load-carrying and anti-wearagents in water-based functional fluids. The nitrogen- andphosphorus-containing compositions are made by the reaction of (A) atleast one carboxylic acid acylating agent, with (B) at least one aminecharacterized by the presence within its structure of at least oneHN<group, and (C) at least one phosphorus-containing acid of the formula##STR1## wherein each X¹, X², X³ and X⁴ is independently oxygen orsulfur, each m is zero or one, and each R¹ and R² is independently ahydrocarbyl group.

European Application 0 156 572 discloses compounds which contain ahydrophobic component and a hydrophilic component covalently bondedtogether which are useful as surfactants in water-in-oil emulsions. Thehydrophobic component is a saturated or unsaturated C₃₀₋₅₀₀ hydrocarbonchain, and the hydrophilic component contains an anionic groupingselected from phosphate, phosphonate, sulphate, sulphonate andcarboxymethyl. Example 1 discloses a compound derived frompoly(isobutenyl) succinic anhydride, ethanolamine, and phosphoric acid.Other examples indicate that diethanolamine or tris(hydroxymethyl)aminoethane can be substituted for the ethanolamine used in Example 1.

Water-in-oil explosive emulsions typically comprise a discontinuousoxidizer phase comprising at least one oxygen-supplying component suchas ammonium nitrate, a continuous organic phase comprising at least onecarbonaceous fuel, and an emulsifier Examples of such water-in-oilexplosive emulsions are disclosed, inter alia, in U.S. Pat. Nos.3,447,978; 3,765,964; 3,985,593; 4,008,110; 4,097,316; 4,104,092;4,110,134; 4,149,916; 4,149,917; 4,218,272; 4,259,977; 4,357,184;4,371,408; 4,391,659; 4,404,050; 4,409,044; 4,448,619; 4,453,989; and4,534,809; and U.K. Patent Application 2,050,340A.

U.S. Pat. No. 4,216,040 discloses water-in-oil emulsion blasting agentshaving a discontinuous aqueous phase, a continuous oil orwater-immiscible liquid organic phase, and an organic cationicemulsifier having a lipophilic portion and a hydrophilic portion, thelipophilic portion being an unsaturated hydrocarbon chain.

U.S. Pat. No. 4,708,753 discloses water-in-oil emulsions which comprise(A) a continuous oil phase; (B) a discontinuous aqueous phase; (C) aminor emulsifying amount of at least one salt derived from (C)(I) atleast one hydrocarbyl-substituted carboxylic acid or anhydride, or esteror amide derivative of said acid or anhydride, the hydrocarbylsubstituent of (C)(I) having an average of from about 20 to about 500carbon atoms, and (C)(II) at least one amine; and (D) a functionalamount of at least one water-soluble, oil-insoluble functional additivedissolved in said aqueous phase. These emulsions can be explosiveemulsions when the functional additive (D) is an oxygen-supplying saltsuch as ammonium nitrate.

U.S. Pat. No. 4,710,248 discloses an emulsion explosive compositioncomprising a discontinuous oxidizer-phase dispersed throughout acontinuous fuel phase with a modifier comprising a hydrophilic moietyand a lipophilic moiety. The hydrophilic moiety comprises a carboxylicacid or a group capable of hydrolyzing to a carboxylic acid. Thelipophilic moiety is a saturated or unsaturated hydrocarbon chain. Theemulsion explosive composition pH is above 4.5.

U.S. Pat. No. 4,822,433 discloses an explosive emulsion compositioncomprising a discontinuous phase containing an oxygen-supplyingcomponent and an organic medium forming a continuous phase wherein theoxygen-supplying component and organic medium are capable of forming anemulsion which, in the absence of a supplementary adjuvant, exhibits anelectrical conductivity measured at 60° C., not exceeding 60,000picomhos/meter. The reference indicates that the conductivity may beachieved by the inclusion of a modifier which also functions as anemulsifier. The modifier is comprised of a hydrophilic moiety and alipophilic moiety. The lipophilic moiety can be derived from apoly[alk(en)yl] succinic anhydride. Poly(isobutylene) succinic anhydridehaving a number average molecular weight in the range of 400 to 5000 isspecifically identified as being useful. The hydrophilic moiety isdescribed as being polar in character, having a molecular weight notexceeding 450 and can be derived from polyols, amines, amides, alkanolamines and heterocyclics. Example 5 of this reference discloses the useas the modifier of a 1:1 condensate of polyisobutenyl succinic anhydride(number average molecular weight=1200) and ethanol amine which had beenreacted with one mole of phosphoric acid to form a monophosphatederivative. The emulsifier disclosed in this example is described asbeing useful in making an emulsion useful for making cartridges.

South African Patent 87/8540 discloses an explosive compositioncomprising a discontinuous oxidizer phase comprising at least oneoxygen-supplying component, a continuous organic phase comprising atleast one water-immiscible organic liquid, and an emulsifying amount ofat least one nitrogen-containing emulsifier derived from (A) at leastone carboxylic acylating agent, (B) at least one polyamine, and (C) atleast one acid or acid-producing compound capable of forming at leastone salt with said polyamine. Examples of (A) include polyisobutenylsuccinic acid or anhydride. Examples of (B) include the alkylenepolyamines. Examples of (C) include the phosphorus acids (e.g.,O,S-dialkylphosphorotrithioic acid). These explosive compositions can bewater-in-oil emulsions or melt-in-oil emulsions.

SUMMARY OF THE INVENTION

The present invention provides for a composition comprising the reactionproduct of component (I) with component (II);

component (I) comprising:

(A) the reaction product of

(A)(i) at least one carboxylic acid or anhydride, or ester or amidederived from said acid or anhydride, with

(A)(ii) ammonia, at least one amine, at least one alkali metal and/or atleast one alkaline-earth metal; or

(B) a composition comprising

(B)(i) the reaction product of (B)(i)(a) at least one high-molecularweight hydrocarbyl-substituted carboxylic acid or anhydride, or ester oramide derived from said high-molecular weight acid or anhydride, with(B)(i)(b) ammonia, at least one amine, at least one alkali metal and/orat least one alkaline-earth metal, component (B)(i)(a) having at leastone hydrocarbyl substituent having an average of about 20 to about 500carbon atoms; and

(B)(ii) the reaction product of (B)(ii)(a) at least one low-molecularweight carboxylic acid or anhydride, or ester or amide derived from saidlow-molecular weight acid or anhydride, with (B)(ii)(b) ammonia, atleast one amine, at least one alkali metal and/or at least onealkaline-earth metal, component (B)(ii)(a) optionally having at leastone hydrocarbyl substituent having an average of up to about 18 carbonatoms; or

(C) a composition comprising

(C)(i) the reaction product of (C)(i)(a) at least one high-molecularweight hydrocarbyl-substituted polycarboxylic acid or anhydride, orester or amide derived from said high-molecular weight polycarboxylicacid or anhydride, with (C)(i)(b) ammonia, at least one amine, at leastone alkali metal and/or at least one alkaline-earth metal, component(C)(i)(a) having at least one hydrocarbyl substituent having an averageof about 20 to about 500 carbon atoms; and

(C)(ii) the reaction product of (C)(ii)(a) at least One low-molecularweight polycarboxylic acid or anhydride, or ester or amide derived fromsaid low-molecular weight polycarboxylic acid or anhydride, with(C)(ii)(b) ammonia, at least one amine, at least one alkali metal and/orat least one alkaline-earth metal, component (C)(ii)(a) optionallyhaving at least one hydrocarbyl substituent having an average of up toabout 18 carbon atoms;

said components (C)(i) and (C)(ii) being coupled together by (C)(iii) atleast one compound having (C)(iii)(a) two or more primary amino groups,(C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least oneprimary amino group and at least one secondary amino group, (C)(iii)(d)at least two hydroxyl groups, or (C)(iii)(e) at least one primary orsecondary amino group and at least one hydroxyl group; or

(D) mixture of two or more of (A), (B) and (C);

component (II) comprising:

(A') at least one phosphorus-containing acid represented by the formula##STR2## wherein X¹, X², X³ and X⁴ are independently oxygen or sulfur; aand b are independently zero or one, and R¹ and R² are independentlyhydrocarbyl groups; or

(B') at least one salt derived from said phosphorous-containing acid(A') and at least one metal selected from the group consisting ofmagnesium, calcium, strontium, chromium, manganese, iron, molybdenum,cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead, andmixtures of two or more thereof; or

(C') mixture of (A') and (B');

with the proviso that when component (II) is (A'), component (I) is (B),(C) or a mixture of (B) and (C). The invention further provides forconcentrates comprising the foregoing composition. The invention furtherprovides for explosive emulsions comprising a discontinuous oxidizerphase comprising at least one oxygen-supplying component, a continuousorganic phase comprising at least one carbonaceous fuel, and anemulsifying amount of the foregoing composition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "emulsion" as used in this specification and in the appendedclaims is intended to cover not only water-in-oil emulsions, but alsoexplosive compositions derived from such emulsions wherein attemperatures below that at which the emulsion is formed thediscontinuous phase is solid or in the form of droplets of super-cooledliquid.

The term "hydrocarbyl" is used herein to include:

(1) hydrocarbyl groups, that is, aliphatic (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic- andalicyclic-substituted aromatic groups and the like as well as cyclicgroups wherein the ring is completed through another portion of themolecule (that is, any two indicated groups may together form analicyclic group);

(2) substituted hydrocarbyl groups, that is, those groups containingnon-hydrocarbon groups which, in the context of this invention, do notalter the predominantly hydrocarbyl nature of the hydrocarbyl group;those skilled in the art will be aware of such groups, examples of whichinclude ether, oxo, halo (e.g., chloro and fluoro), alkoxyl, mercapto,alkylmercapto, nitro, nitroso, sulfoxy, etc.;

(3) hetero groups, that is, groups which will, while havingpredominantly hydrocarbyl character within the context of thisinvention, contain other than carbon present in a ring or chainotherwise composed of carbon atoms. Suitable heteroatoms will beapparent to those of skill in the art and include, for example, sulfur,oxygen, nitrogen and such substituents as pyridyl, furanyl, thiophenyl,imidazolyl, etc.

In general, no more than about three non-hydrocarbon groups orheteroatoms and preferably no more than one, will be present for each 10carbon atoms in a hydrocarbyl group. Typically, there will be no suchgroups or heteroatoms in a hydrocarbyl group and it will, therefore, bepurely hydrocarbyl.

The hydrocarbyl groups are preferably free from acetylenic unsaturation;ethylenic unsaturation, when present will generally be such that thereis no more than one ethylenic linkage present for every 10carbon-to-carbon bonds. The hydrocarbyl groups are often completelysaturated and therefore contain no ethylenic unsaturation.

The term "lower" as used herein in conjunction with terms such as alkyl,alkenyl, alkoxy, and the like, is intended to describe such groups whichcontain a total of up to 7 carbon atoms.

The term "water-soluble" refers to materials which are soluble in waterto the extent of at least one gram per 100 milliliters of water at 25°C.

The term "oil-soluble" referes to materials which are soluble in mineraloil to the extent of at least one gram per 100 milliliters of oil at 25°C.

Component (A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a)

Components (B)(i)(a) and (C)(i)(a) are high-molecular weighthydrocarbyl-substituted carboxylic acids or anhydrides, or esters oramides derived therefrom. Typically these high-molecular weight acids oranhydrides or derivatives have hydrocarbyl substituents containing anaverage of about 20 to about 500 carbon atoms, more preferably about 30to about 500 carbon atoms, more preferably about 40 to about 500 carbonatoms, more preferably about 50 to about 500 carbon atoms.

Components (B)(ii)(a) and (C)(ii)(a) are low-molecular weight carboxylicacids or anhydrides, or esters or amides derived therefrom. Theselow-molecular weight acids or anhydrides or derivatives can optionallyinclude a hydrocarbyl substituent of up to about 18 carbon atoms,preferably about 4 to about 18 carbon atoms, more preferably about 8 toabout 18 carbon atoms, more preferably about 10 to about 18 carbonatoms, more preferably about 12 to about 18 carbon atoms, morepreferably about 16 to about 18 carbon atoms. The hydrocarbylsubstituent can be derived from at least one compound selected from thegroup consisting of ethylene, propylene, 1-butene, isobutene, 1-pentene,2-methyl-1butene, 3-methyl-1-butene, 1-hexene, 1-heptene, 1-octene,styrene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene and1-octadecene. The hydrocarbyl substituent can be derived from analpha-olefin fractions such as those selected from the group consistingof C₁₅₋₁₈ alpha-olefins, C₁₂₋₁₆ alpha-olefins, C₁₄₋₁₆ alpha-olefins,C₁₄₋₁₈ alpha-olefins, C₁₆₋₁₈ alpha-olefins, etc.

Component (A)(i) can be either a low-molecular weight or ahigh-molecular weight carboxylic acid or anhydride, or ester or amidederived therefrom. When the inventive compositions are used asemulsifiers for explosive emulsions, such compositions are soluble inthe organic phase of such emulsions. The number of carbon atoms presentin component (A)(i) is important in contributing to the desiredsolubility of these compositions. The sum of the carbon atoms incomponents (I) and (II) must be sufficient to render the compositionoil-soluble. Generally, if component (A)(i) contains a large number ofcarbon atoms, components (A)(ii) and (II) may be selected from thosecompounds containing fewer carbon atoms. Conversely, if components(A)(ii) and/or (II) contain a large number of carbon atoms, component(A)(i) can be selected from those compounds containing fewer carbonatoms. Usually, in order to provide the desired hydrocarbon solubility,the sum of the carbon atoms in components (A)(i), (A)(ii) and (II)should total at least about 10 carbon atoms, more preferably at leastabout 30 carbon atoms, more preferably at least about 50 carbon atoms.

Components (A)(i), (B)(i)(a) and (B)(ii)(a) can be mono- orpolycarboxylic acids or anhydrides, or esters or amides derivedtherefrom. Components (C)(i)(a) and (C)(ii)(a) are polycarboxylic acidsor anhydrides, or esters or amides derived therefrom. Each of thesecomponents can be aliphatic or aromatic. These components may containpolar substituents provided that the polar substituents are not presentin portions sufficiently large to alter significantly the hydrocarboncharacter of the acylating agent. Typical suitable polar substituentsinclude halo, such as chloro and bromo, oxo, oxy, formyl, sulfenyl,sulfinyl, thio, nitro, etc. Such polar substituents, if present,preferably do not exceed about 10% by weight of the total weight of thehydrocarbon portion of these components, exclusive of the carboxylgroups.

The low-molecular weight monocarboxylic acids contemplated for use inthis invention include saturated and unsaturated acids. Examples of suchuseful acids include formic acid, acetic acid, chloroacetic acid,propionic acid, butyric acid, acrylic, benzoic acid, butanoic acid,cyclohexanoic, dodecanoic acid, palmitic acid, decanoic acid, oleicacid, lauric acid, stearic acid, myristic acid, linoleic acid, linolenicacid, naphthenic acid, chlorostearic acid, tall oil acid, etc.Anhydrides as well as esters and amides derived from these acids canalso be used. Mixtures of two or more of the foregoing can also be used.

Examples of low-molecular weight polycarboxylic acids and anhydridesthat can be used include dicarboxylic acids and derivatives such asmaleic acid, maleic anhydride, chloromaleic anhydride, malonic acid,succinic acid, succinic anhydride, glutaric acid, glutaric anhydride,adipic acid, pimelic acid, azelaic acid, sebacic acid, glutaconic acid,citraconic acid, itaconic acid, allyl succinic acid, cetyl malonic acid,tetrapropylene-substituted succinic anhydride, etc. Esters and amidesderived from these acids and anhydrides can be used.

An extensive discussion of these low-molecular weight carboxylic acidscan be found in Kirk-Othmer "Encyclopedia of Chemical Technology" ThirdEdition, 1978, John Wiley & Sons, New York, pp. 814-871; these pagesbeing incorporated herein by reference.

Low-molecular weight hydrocarbyl-substituted succinic acid andanhydrides can be used. These acids and anhydrides can be represented bythe formulae ##STR3## wherein R is a hydrocarbyl group of up to about 18carbon atoms, preferably about 4 to about 18 carbon atoms, morepreferably about 8 to about 18 carbon atoms, more preferably about 10 toabout 18 carbon atoms, more preferably about 12 to about 18 carbonatoms, more preferably about 16 to about 18 carbon atoms. Preferably, Ris an aliphatic or alicyclic hydrocarbyl group with less than 10% of itscarbon-to-carbon bonds being unsaturated. Examples of such groupsinclude 4-butylcyclohexyl, di(isobutyl), decyl, etc. The hydrocarbylgroup can be derived from an olefin such as ethylene, propylene,1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene,1-hexene, 1-heptene, 1-octene, styrene, 1-nonene, 1-decene, 1-undecene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, etc. The hydrocarbyl group can also bederived from an olefin fraction such as C₁₅₋₁₈ alpha-olefins, C₁₂₋₁₆alpha-olefins, C₁₄₋₁₆ alpha-olefins, C₁₄₋₁₈ alpha-olefins, C₁₆₋₁₈alphaolefins, etc.

The monocarboxylic acids include isoaliphatic acids, i.e., acids havingone or more lower acyclic pendant alkyl groups. Such acids often containa principal chain having from about 14 to about 20 saturated, aliphaticcarbon atoms and at least one but usually no more than about fourpendant acyclic alkyl groups. These acids are categorized aslow-molecular weight or high-molecular weight acids within the scope ofthe invention depending upon the total number of carbon atoms in theprincipal chain and pendant groups; low-molecular weight acids have upto about 18 carbon atoms, while high-molecular weight acids have about20 or more carbon atoms. The principal chain of the acid is exemplifiedby groups derived from tetradecane, pentadecane, hexadecane,heptadecane, octadecane, and eicosane. The pendant group is preferably alower alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, n-hexyl, or other groups having up to about 7carbon atoms. The pendant group may also be a polar-substituted alkylgroup such as chloromethyl, bromobutyl, methoxyethyl, or the like, butit preferably contains no more than one polar substituent per group.Specific examples of such isoaliphatic acids include10-methyl-tetradecanoic acid, 11-methyl-pentadecanoic acid,3-ethyl-hexadecanoic acid, 15-methyl-heptadecanoic acid,16-methyl-heptadecanoic acid, 6-methyl-octadecanoic acid,8-methyl-octadecanoic acid, 10-methyl-octadecanoic acid,14-methyl-octadecanoic acid, 16-methyloctadecanoic acid,15-ethyl-heptadecanoic acid, 3-chloromethyl-nonadecanoic acid,7,8,9,10-tetramethyl-octadecanoic acid, and2,9,10-trimethyl-octadecanoic acid.

The isoaliphatic acids include mixtures of branch-chain acids preparedby the isomerization of commercial fatty acids of, for example, about 16to about 20 carbon atoms. A useful method involves heating the fattyacid at a temperature above about 250° C. and a pressure between about200 and 700 psi, distilling the crude isomerized acid, and hydrogenatingthe distillate to produce a substantially saturated isomerized acid. Theisomerization can be promoted by a catalyst such as mineral clay,diatomaceous earth, aluminum chloride, zinc chloride, ferric chloride,or some other Friedel-Crafts catalyst. The concentration of the catalystmay be as low as about 0.01%, but more often from about 0.1% to about 3%by weight of the isomerization mixture. Water also promotes theisomerization and a small amount, from about 0.1% to about 5% by weight,of water may thus be advantageously added to the isomerization mixture.The unsaturated fatty acids from which the isoaliphatic acids may bederived include oleic acid, linoleic acid, linolenic acid, andcommercial fatty acid mixtures such as tall oil acids.

The high-molecular weight mono- and polycarboxylic acids and anhydridesare well known in the art and have been described in detail, forexample, in the following U.S., British and Canadian patents: U.S. Pat.Nos. 3,024,237; 3,087,936; 3,163,603; 3,172,892; 3,215,707; 3,219,666;3,231,587; 3,245,910; 3,254,025; 3,271,310; 3,272,743; 3,272,746;3,278,550; 3,288,714; 3,306,907; 3,307,928; 3,312,619; 3,341,542;3,346,354; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179;3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169;3,868,330; 3,912,764; 4,234,435; and 4,368,133; British Pat. Nos.944,136; 1,085,903; 1,162,436; and 1,440,219; and Canadian Pat. No.956,397. These patents are incorporated herein by reference for theirdisclosures of such acids and anhydrides and the methods for makingthem.

As disclosed in the foregoing patents, there are several processes forpreparing these high-molecular weight acids and anhydrides. Generally,these processes involve the reaction of (1) an ethylenically unsaturatedcarboxylic acid, acid halide, anhydride or ester reactant with (2) anethylenically unsaturated hydrocarbon or a chlorinated hydrocarbon at atemperature within the range of about 100°-300° C. The chlorinatedhydrocarbon or ethylenically unsaturated hydrocarbon reactant preferablycontains at least about 10 carbon atoms, more preferably at least about20 carbon atoms, more preferably at least about 30 carbon atoms, morepreferably at least about 40 carbon atoms, more preferably at leastabout 50 carbon atoms, and may contain polar substituents,oil-solubilizing pendant groups, and be unsaturated within the generallimitations explained hereinabove.

When preparing the hydrocarbyl-substituted carboxylic acids, thecarboxylic acid reactant usually corresponds to the formula R_(o)-(COOH)_(n), where R_(o) is characterized by the presence of at leastone ethylenically unsaturated carbon-to-carbon covalent bond and n is aninteger from 1 to about 6 and preferably 1 or 2. The acidic reactant canalso be the corresponding carboxylic acid halide, anhydride, ester, orother equivalent acylating agent and mixtures of one or more of these.Ordinarily, the total number of carbon atoms in the acidic reactant willnot exceed about 20, preferably this number will not exceed about 10 andgenerally will not exceed about 6. Preferably the acidic reactant willhave at least one ethylenic linkage in an alpha-, beta-position withrespect to at least one carboxyl function. Exemplary acidic reactantsare acrylic acid, methacrylic acid, maleic acid, maleic anhydride,fumaric acid, itaconic acid, itaconic anhydride, citraconic acid,citraconic anhydride, mesaconic acid, glutaconic acid, chloromaleicacid, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid,3-hexenoic acid, 10-decenoic acid, and the like. Preferred acidreactants include acrylic acid, methacrylic acid, maleic acid, andmaleic anhydride.

The ethylenically unsaturated hydrocarbon reactant and the chlorinatedhydrocarbon reactant used in the preparation of these high-molecularweight carboxylic acids and anhydrides can be high molecular weight,substantially saturated petroleum fractions and substantially saturatedolefin polymers and the corresponding chlorinated products. Polymers andchlorinated polymers derived from mono-olefins having from 2 to about 30carbon atoms, preferably 2 to about 20 carbon atoms, more preferably 2to about 12 carbon atoms, more preferably 2 to about 8 carbon atoms,more preferably 2 to about 6 carbon atoms are useful. Useful polymersare the polymers of 1-mono-olefins such as ethylene, propene, 1-butene,isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene,3-cyclohexyl-1-butene, and 2-methyl-5-propyl-1-hexene. Polymers ofmedial olefins, i.e., olefins in which the olefinic linkage is not atthe terminal position, likewise are useful. These are exemplified by2-butene, 3-pentene, 4-octene, etc.

Interpolymers of 1-mono-olefins such as illustrated above with eachother and with other interpolymerizable olefinic substances such asaromatic olefins, cyclic olefins, and polyolefins, are also usefulsources of the ethylenically unsaturated reactant. Such interpolymersinclude for example, those prepared by polymerizing isobutene withstyrene, isobutene with butadiene, propene with isoprene, propene withisobutene, ethylene with piperylene, isobutene with chloroprene,isobutene with p-methyl-styrene, 1-hexene with 1,3-hexadiene, 1-octenewith 1-hexene, 1-heptene with 1-pentene, 3-methyl-1-butene with1-octene, 3,3-dimethyl-1-pentene with 1-hexene, isobutene with styreneand piperylene, etc.

For reasons of hydrocarbon solubility, the interpolymers contemplatedfor use in preparing the high-molecular weight carboxylic acids andanhydrides of this invention are preferably substantially aliphatic andsubstantially saturated. That is, they should contain at least about 80%and preferably at least about 95%, on a weight basis, of units derivedfrom aliphatic mono- olefins. Preferably, they contain no more thanabout 5% olefinic linkages based on the total number of thecarbon-to-carbon covalent linkages present.

In one embodiment of the invention, the polymers and chlorinatedpolymers are obtained by the polymerization of a C₄ refinery streamhaving a butene content of about 35% to about 75% by weight and anisobutene content of about 30% to about 60% by weight in the presence ofa Lewis acid catalyst such as aluminum chloride or boron trifluoride.These polyisobutenes preferably contain predominantly (that is, greaterthan about 80% of the total repeat units) isobutene repeat units of theconfiguration. ##STR4##

The chlorinated hydrocarbons and ethylenically unsaturated hydrocarbonsused in the preparation of the high-molecular weight carboxylic acidsand anhydrides preferably have up to about 500 carbon atoms permolecule. Preferred high-molecular weight carboxylic acids andanhydrides are those containing hydrocarbyl groups of from about 20 toabout 500 carbon atoms, more preferably from about 30 to about 500carbon atoms, more preferably from about 40 to about 500 carbon atoms,more preferably from about 50 to about 500 carbon atoms.

The high-molecular weight carboxylic acids and anhydrides may also beprepared by halogenating a high molecular weight hydrocarbon such as theabove-described olefin polymers to produce a polyhalogenated product,converting the polyhalogenated product to a polynitrile, and thenhydrolyzing the polynitrile. They may be prepared by oxidation of a highmolecular weight polyhydric alcohol with potassium permanganate, nitricacid, or a similar oxidizing agent. Another method involves the reactionof an olefin or a polar-substituted hydrocarbon such as achloropolyisobutene with an unsaturated polycarboxylic acid such as2-pentene-1,3,5-tricarboxylic acid prepared by dehydration of citricacid.

The high-molecular weight carboxylic acid and anhydrides can also beobtained by reacting chlorinated carboxylic acids, anhydrides, acylhalides, and the like with ethylenically unsaturated hydrocarbons orethylenically unsaturated substituted hydrocarbons such as thepolyolefins and substituted polyolefins described hereinbefore in themanner described in U.S. Pat. No. 3,340,281, this patent beingincorporated herein by reference.

The low- and high-molecular weight carboxylic acid anhydrides can beobtained by dehydrating the corresponding acids. Dehydration is readilyaccomplished by heating the acid to a temperature above about 70° C.,preferably in the presence of a dehydration agent, e.g., aceticanhydride. Cyclic anhydrides are usually obtained from polycarboxylicacids having acid groups separated by no more than three carbon atomssuch as substituted succinic or glutaric acid, whereas linear anhydridesare usually obtained from polycarboxylic acids having the acid groupsseparated by four or more carbon atoms.

The low-molecular weight and high-molecular weight carboxylic acids usedherein include acid-producing derivatives thereof (in addition to theanhydrides) such as acyl halides and the like. Thus, the term"carboxylic acid" when used in the claims herein also refers to the acylhalides of such acids. These acyl halides can be prepared by thereaction of the carboxylic acids or their anhydrides with a halogenatingagent such as phosphorus tribromide, phosphorus pentachloride or thionylchloride using known techniques.

Hydrocarbyl-substituted succinic acids and anhydrides are preferredhigh-molecular weight carboxylic acids and anhydrides. These acids andanhydrides can be prepared by reacting maleic anhydride with an olefinor a chlorinated hydrocarbon such as a chlorinated polyolefin. Thereaction involves merely heating the two reactants at a temperature inthe range of about 100° C. to about 300° C., preferably, about 100° C.to about 200° C. The product from this reaction is ahydrocarbyl-substituted succinic anhydride wherein the substituent isderived from the olefin or chlorinated hydrocarbon. The product may behydrogenated to remove all or a portion of any ethylenically unsaturatedcovalent linkages by standard hydrogenation procedures, if desired. Thehydrocarbyl-substituted succinic anhydrides may be hydrolyzed bytreatment with water or steam to the corresponding acid. Thehigh-molecular weight hydrocarbyl-substituted succinic acids andanhydrides can be represented by the formulae ##STR5## wherein R is thehydrocarbyl substituent. Preferably R contains from about 20 to about500 carbon atoms, more preferably from about 30 to about 500 carbonatoms, more preferably from about 40 to about 500 carbon atoms, morepreferably from about 50 to about 500 carbon atoms.

The Alcohols Useful In Making the Carboxylic Acid Ester Derivatives(A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a)

The alcohols useful in making the carboxylic acid ester derivatives(A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a) of thisinvention include those compounds of the general formula:

    R.sub.1 --(OH).sub.m

wherein R₁ is a monovalent or polyvalent organic group joined to the--OH groups through carbon-to-oxygen bonds (that is, --COH wherein thecarbon is not part of a carbonyl group) and m is an integer of from 1 toabout 10, preferably 2 to about 6. These alcohols can be aliphatic,cycloaliphatic, aromatic, and heterocyclic, includingaliphatic-substituted cycloaliphatic alcohols, aliphatic-substitutedaromatic alcohols, aliphatic-substituted heterocyclic alcohols,cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted heterocyclic alcohols,heterocyclic-substituted aliphatic alcohols, heterocyclic-substitutedcycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols.Except for the polyoxyalkylene alcohols, the mono- and polyhydricalcohols corresponding to the formula R₁ (OH)_(m) preferably contain notmore than about 40 carbon atoms, more preferably not more than about 20carbon atoms. The alcohols may contain non-hydrocarbon substituents orgroups which do not interfere with the reaction of the alcohols with thehydrocarbyl-substituted carboxylic acids or anhydrides of thisinvention. Such non-hydrocarbon substituents or groups include loweralkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as--O-- and --S-- (e.g., as in such groups as --CH₂ CH₂ --X--CH₂ CH₂ --where X is --O-- or --S--).

Among the polyoxyalkylene alcohols suitable for use in the preparationof the ester derivatives of this invention are the commerciallyavailable polyoxyalkylene alcohols that include the polyoxyethylatedamines, amides, and quaternary salts available from Armour IndustrialChemical Co. under the names ETHODUOMEEN polyethoxylatedhigh-molecular-weight aliphatic diamines; ETHOMEEN, polyethoxylatedaliphatic amines containing alkyl groups in the range of about 8 toabout 18 carbon atoms; ETHOMID, polyethoxylated high-molecular-weightamides; and ETHOQUAD, polyethoxylated quaternary ammonium chloridesderived from long-chain amines.

Useful polyoxyalkylene alcohols and derivatives thereof include thehydrocarbyl ethers and the carboxylic acid esters obtained by reactingthe alcohols with various carboxylic acids. Illustrative hydrocarbylgroups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc.,containing up to about 40 carbon atoms. Specific hydrocarbyl groupsinclude methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl,p-octylphenyl ethyl, cyclohexyl, and the like. Carboxylic acids usefulin preparing the ester derivatives are mono- or polycarboxylic acidssuch as acetic acid, valeric acid, lauric acid, stearic acid, succinicacid, and alkyl or alkenyl-substituted succinic acids wherein the alkylor alkenyl group contains up to about 20 carbon atoms. Members of thisclass of alcohols are commercially available from various sources; e.g.,PLURONICS, polyols available from Wyandotte Chemicals Corporation;POLYGLYCOL 112-2, a liquid triol derived from ethyleneoxide andpropylene-oxide available from Dow Chemical Co.; and TERGITOLS,dodecylphenyl or nonylphenyl polyethylene glycol ethers, and UCONS,polyalkylene glycols and various derivatives thereof, both availablefrom Union Carbide Corporation. However, the alcohols used must have anaverage of at least one free alcoholic hydroxyl group per molecule ofpolyoxyalkylene alcohol. For purposes of describing thesepolyoxyalkylene alcohols, an alcoholic hydroxyl group is one attached toa carbon atom that does not form part of an aromatic nucleus.

Alcohols useful in this invention also include alkylene glycols andpolyoxyalkylene alcohols such as polyoxyethylene alcohols,polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. Thesepolyoxyalkylene alcohols (sometimes called polyglycols) can contain upto about 150 oxyalkylene groups, with the alkylene group containing fromabout 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols aregenerally dihydric alcohols. That is, each end of the moleculeterminates with an OH group. In order for such polyoxyalkylene alcoholsto be useful, there must be at least one such OH group. However, theremaining OH group can be esterified with a monobasic, aliphatic oraromatic carboxylic acid of up to about 20 carbon atoms such as aceticacid, propionic acid, oleic acid, stearic acid, benzoic acid, and thelike. The monoethers of these alkylene glycols and polyoxyalkyleneglycols are also useful. These include the monoaryl ethers, monoalkylethers, and monoaralkyl ethers of these alkylene glycols andpolyoxyalkylene glycols. This group of alcohols can be represented bythe formula

    HO--(--R.sub.A O--).sub.p R.sub.B --OR.sub.C

wherein R_(A) and R_(B) are independently alkylene groups of from about2 to 8 carbon atoms; and R_(C) is aryl (e.g., phenyl), lower alkoxyphenyl, or lower alkyl phenyl, or lower alkyl (e.g., ethyl, propyl,terbutyl, pentyl, etc.); and aralkyl (e.g., benzyl, phenylethyl,phenylpropyl, p-ethylphenylethyl, etc.); p is from zero to about eight,preferably from about 2 to 4. Polyoxyalkylene glycols where the alkylenegroups are ethylene or propylene and p is at least two as well as themonoethers thereof as described above are useful.

The monohydric and polyhydric alcohols useful in this invention includemonohydroxy and polyhydroxy aromatic compounds. Monohydric andpolyhydric phenols and naphthols are preferred hydroxyaromaticcompounds. These hydroxy-substituted aromatic compounds may containother substituents in addition to the hydroxy substituents such as halo,alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like. Usually, thehydroxy aromatic compound will contain from 1 to about 4 hydroxy groups.The aromatic hydroxy compounds are illustrated by the following specificexamples: phenol, p-chlorophenol, p-nitrophenol, beta-naphthol,alpha-naphthol, cresols, resorcinol, catechol, carvacrol, thymol,eugenol, p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol,phloroglucinol, hexylresorcinol, orcin, quaiacol, 2-chlorophenol,2,4-dibutylphenol, propene-tetramer-substituted phenol, didodecylphenol,4,4'-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-naphthol,polyisobutenyl-(molecular weight of about 1000)-substituted phenol, thecondensation product of heptylphenol with about 0.5 mole offormaldehyde, the condensation product of octylphenol with acetone,di(hydroxyphenyl)oxide, di-(hydroxyphenyl)sulfide,di(hydroxyphenyl)-disulfide, and 4-cyclohexylphenol. Phenol itself andaliphatic hydrocarbonsubstituted phenols, e.g., alkylated phenols havingup to 3 aliphatic hydrocarbon substituents are useful. Each of thealiphatic hydrocarbon substituents may contain about 100 or more carbonatoms but usually will have from 1 to about 20 carbon atoms. Alkyl andalkenyl groups are the preferred aliphatic hydrocarbon substituents.

Further specific examples of monohydric alcohols which can be usedinclude monohydric alcohols such as methanol, ethanol, isooctanol,dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol,hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol,beta-phenylethyl alcohol, 2-methylcyclohexanol, beta-chloroethanol,monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol,monopropyl ether of diethylene glycol, monododecyl ether of triethyleneglycol, monooleate of ethylene glycol, monostearate of diethyleneglycol, sec-pentyl alcohol, tertbutyl alcohol, 5-bromo-dodecanol,nitro-octadecanol, and dioleate of glycerol. Alcohols useful in thisinvention may be unsaturated alcohols such as allyl alcohol, cinnamylalcohol, 1-cyclohexene-3-ol and oleyl alcohol.

Other specific alcohols useful in this invention are the ether alcoholsand amino alcohols including, for example, the oxyalkylene-,oxyarylene-, aminoalkylene-, and amino-arylene-substituted alcoholshaving one or more oxyalkylene, aminoalkylene oramino-arylene-oxy-arylene groups. These alcohols are exemplified by theCellosolves, (products of Union Carbide identified as mono- and dialkylethers of ethylene glycol and their derivatives), the Carbitols(products of Union Carbide identified as mono- and dialkyl ethers ofdiethylene glycol and their derivatives), phenoxyethanol,heptyl-phenyl-(oxypropylene)₆ --OH, octyl-(oxyethylene)₃₀ --OH,phenyl-(oxyoctylene)₂ --OH, mono-(heptylphenyloxypropylene)-substitutedglycerol, poly(styreneoxide), amino-ethanol, 3-aminoethylpentanol,di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine,N-hydroxyethyl ethylenediamine,N,N,N',N'-tetrahydroxytrimethylenediamine, and the like.

The polyhydric alcohols preferably contain from 2 to about 10 hydroxygroups. They are illustrated, for example, by the alkylene glycols andpolyoxyalkylene glycols mentioned above such as ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropylene glycol, dibutylene glycol, tributylene glycol, andother alkylene glycols and polyoxyalkylene glycols in which the alkylenegroups contain from 2 to about 8 carbon atoms.

Other useful polyhydric alcohols include glycerol, monooleate ofglycerol, monostearate of glycerol, monomethyl ether of glycerol,pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methylester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol,2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol,1,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugars,starches, celluloses, and so forth likewise can be used. Thecarbohydrates may be exemplified by glucose, fructose, sucrose, rhamose,mannose, glyceraldehyde, and galactose.

Polyhydric alcohols having at least 3 hydroxyl groups, some, but not allof which have been esterified with an aliphatic monocarboxylic acidhaving from about 8 to about 30 carbon atoms such as octanoic acid,oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oilacid are useful. Further specific examples of such partially esterifiedpolyhydric alcohols are the monooleate of sorbitol, distearate ofsorbitol, monooleate of glycerol, monostearate of glycerol,di-dodecanoate of erythritol, and the like.

Useful alcohols also include those polyhydric alcohols containing up toabout 12 carbon atoms, and especially those containing from about 3 toabout 10 carbon atoms. This class of alcohols includes glycerol,erythritol, pentaerythritol, dipentaerythritol, gluconic acid,glyceraldehyde, glucose, arabinose, 1,7-heptanediol, 2,4-heptanediol,1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol,2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid,2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decanediol,digitalose, and the like. Aliphatic alcohols containing at least about 3hydroxyl groups and up to about 10 carbon atoms are useful.

Useful polyhydric alcohols are the polyhydric alkanols containing fromabout 3 to about 10 carbon atoms and particularly, those containingabout 3 to about 6 carbon atoms and having at least three hydroxylgroups. Such alcohols are exemplified by glycerol, erythritol,pentaerythritol, mannitol, sorbitol,2-hydroxymethyl-2-methyl-1,3-propanediol-(trimethylolethane),2-hydroxymethyl-2-ethyl-1,3-propanediol-(trimethylpropane),1,2,4-hexanetriol, and the like.

The carboxylic acids or anhydrides can be reacted with the alcoholsaccording to conventional esterification techniques to form the esterderivatives. This normally involves heating the acid or anhydride withthe alcohol, optionally in the presence of a normally liquid,substantially inert, organic liquid solvent/diluent and/or in thepresence of esterification catalyst. Temperatures of at least about 30°C. up to the decomposition temperature of the reaction component and/orproduct having the lowest such temperature can be used. This temperatureis preferably in the range of about 50° C. to about 130° C., morepreferably about 80° C. to about 100° C. when a carboxylic anhydride isused as the carboxylic reactant. On the other hand, when the carboxylicreactant is an acid, the temperature is preferably in the range of about100° C. up to about 300° C. with temperatures of about 140° C. to 250°C. often being employed. Usually, up to about 0.95 equivalent,preferably from about 0.05 to about 0.95 equivalent of alcohol are usedfor each equivalent of acid or anhydride. Preferably, about 0.5equivalent of alcohol per equivalent of acid or anhydride is employed Anequivalent of an alcohol is its molecular weight divided by the totalnumber of hydroxyl groups present in the molecule. Thus, an equivalentweight of ethanol is its molecular weight while the equivalent weight ofethylene glycol is one-half its molecular weight. The number ofequivalents of the acid or anhydride depends on the total number ofcarboxylic functions (e.g., carboxylic acid or carboxylic anhydridegroups) present in the acid or anhydride. Thus, the number ofequivalents of the acid or anhydride will vary with the number ofcarboxy groups present therein. In determining the number of equivalentsof the acid or anhydride, those carboxyl functions which are not capableof reacting as a carboxylic acid acylating agent are excluded. Ingeneral, however, there is one equivalent of acid or anhydride for eachcarboxy group in the acid or anhydride. For example, there would be twoequivalents in an anhydride derived from the reaction of one mole ofolefin polymer and one mole of maleic anhydride. Conventional techniquesare readily available for determining the number of carboxyl functions(e.g., acid number, saponification number) and, thus, the number ofequivalents of acid or anhydride available to react with the alcohol canbe readily determined by one skilled in the art.

Many issued patents disclose procedures for reacting carboxylic acidsand anhydrides with alcohols to produce acidic esters and neutralesters. These same techniques are applicable to preparing the esters ofthis invention. All that is required is that the acid and/or anhydrideof this invention is substituted for the carboxylic acid acylatingreagents discussed in these patents, usually on an equivalent weightbasis. The following U.S. Patents are expressly incorporated herein byreferences for their disclosure of suitable methods for the preparationof such esters: U.S. Pat. Nos. 3,331,776; 3,381,022; 3,522,179;3,542,680; 3,697,428; and 3,755,169.

The Amines Useful In Making the Amide Derivatives (A)(i), (B)(i)(a),(B)(ii)(a), (C)(i)(a) and (C)(ii)(a)

The amines useful in making the carboxylic acid amide derivatives(A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a) include primaryamines and secondary amines. Ammonia can also be used. The amines arecharacterized by the presence within their structure of at least oneH--N<group and/or at least one --NH₂ group. These amines can bemonoamines or polyamines. Hydrazine and substituted hydrazinescontaining up to three substituents are included as amines suitable forpreparing the amide derivatives. Mixtures of two or of the foregoing canbe used.

The amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic,including aliphatic-substituted aromatic, aliphatic-substitutedcycloaliphatic, aliphatic-substituted heterocyclic,cycloaliphatic-substituted aliphatic, cycloaliphatic-substitutedaromatic, cycloaliphatic-substituted heterocyclic, aromatic-substitutedaliphatic, aromatic-substituted cycloaliphatic, aromatic-substitutedheterocyclic, heterocyclic-substituted aliphatic,heterocyclic-substituted cycloaliphatic and heterocyclic-substitutedaromatic amines. These amines may be saturated or unsaturated. Ifunsaturated, the amine is preferably free from acetylenic unsaturation.The amines may also contain non-hydrocarbon substituents or groups aslong as these groups do not significantly interfere with the reaction ofthe amines with the carboxylic acids and derivatives thereof of thisinvention. Such non-hydrocarbon substituents or groups include loweralkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as--O-- and --S-- (e.g., as in such groups as --CH₂ CH₂ --X--CH₂ CH₂ --where X is --O-- or --S--).

With the exception of the branched polyalkylene polyamines, thepolyoxyalkylene polyamines and the high molecular weighthydrocarbyl-substituted amines described more fully hereinafter, theamines used in this invention ordinarily contain less than about 40carbon atoms in total and usually not more than about 20 carbon atoms intotal.

Aliphatic monoamines include mono-aliphatic and di-aliphatic-substitutedamines wherein the aliphatic groups can be saturated or unsaturated andstraight or branched chain. Thus, they are primary or secondaryaliphatic amines. Such amines include, for example, mono- anddi-alkyl-substituted amines, mono- and di-alkenyl-substituted amines,and amines having one N-alkenyl substituent and one N-alkyl substituent,and the like. The total number of carbon atoms in these aliphaticmonoamines preferably does not exceed about 40 and usually does notexceed about 20 carbon atoms. Specific examples of such monoaminesinclude ethylamine, di-ethylamine, n-butylamine, di-n-butylamine,allylamine, isobutylamine, cocoamine, stearylamine, laurylamine,methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine,octadecylamine, and the like. Examples of cycloaliphatic-substitutedaliphatic amines, aromatic-substituted aliphatic amines, andheterocyclic-substituted aliphatic amines, include2-(cyclohexyl)ethylamine, benzylamine, phenylethylamine, and3-(furylpropyl) amine.

Cycloaliphatic monoamines are those monoamines wherein there is onecycloaliphatic substituent attached directly to the amino nitrogenthrough a carbon atom in the cyclic ring structure. Examples ofcycloaliphatic monoamines include cyclohexylamines, cyclopentylamines,cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamines,dicyclohexylamines, and the like. Examples of aliphatic-substituted,aromatic-substituted, and heterocyclic-substituted cycloaliphaticmonoamines include propyl-substituted cyclohexylamines,phenyl-substituted cyclopentylamines and pyranyl-substitutedcyclohexylamine.

Suitable aromatic amines include those monoamines wherein a carbon atomof the aromatic ring structure is attached directly to the aminonitrogen. The aromatic ring will usually be a mononuclear aromatic ring(i.e., one derived from benzene) but can include fused aromatic rings,especially those derived from naphthylene. Examples of aromaticmonoamines include aniline, di(para-methylphenyl) amine, naphthylamine,N-(n-butyl) aniline, and the like. Examples of aliphatic-substituted,cycloaliphatic-substituted, and heterocyclic-substituted aromaticmonoamines include paraethoxyaniline, paradodecylamine,cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.

Suitable polyamines include aliphatic, cycloaliphatic and aromaticpolyamines analogous to the above-described monoamines except for thepresence within their structure of another amino nitrogen. The otheramino nitrogen can be a primary, secondary or tertiary amino nitrogen.Examples of such polyamines include N-aminopropyl-cyclohexylamine,N-N'-di-n-butylpara-phenylene diamine, bis-(para-aminophenyl)-methane,1,4-diaminocyclohexane, and the like.

Heterocyclic mono- and polyamines can also be used. As used herein, theterminology "heterocyclic mono- and polyamine(s)" is intended todescribe those heterocyclic amines containing at least one primary orsecondary amino group and at least one nitrogen as a heteroatom in theheterocyclic ring. However, as long as there is present in theheterocyclic mono- and polyamines at least one primary or secondaryamino group, the hetero-N atom in the ring can be a tertiary aminonitrogen; that is, one that does not have hydrogen attached directly tothe ring nitrogen. Heterocyclic amines can be saturated or unsaturatedand can contain various substituents such as nitro, alkoxy, alkylmercapto, alkyl, alkenyl, aryl, alkaryl, or aralkyl substituents.Generally, the total number of carbon atoms in the substituents will notexceed about 20. Heterocyclic amines can contain heteroatoms other thannitrogen, especially oxygen and sulfur. Obviously they can contain morethan one nitrogen heteroatom. The 5- and 6-membered heterocyclic ringsare preferred.

Among the suitable heterocyclics are aziridines, azetidines, azolidines,tetra- and di-hydropyridines, pyrroles, indoles, piperadines,imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles,purines, morpholines, thiomorpholines, N-aminoalkylmorpholines,N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,N,N'-di-aminoalkylpiperazines, azepines, azocines, azonines, azecinesand tetra-, di- and per-hydro-derivatives of each of the above andmixtures of two or more of these heterocyclic amines. Preferredheterocyclic amines are the saturated 5- and 6-membered heterocyclicamines containing only nitrogen, oxygen and/or sulfur in the heteroring, especially the piperidines, piperazines, thiomorpholines,morpholines, pyrrolidines, and the like. Piperidine,aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substitutedpiperazines, morpholine, aminoalkyl-substituted morpholines,pyrrolidine, and aminoalkyl-substituted pyrrolidines, are useful.Usually the aminoalkyl substituents are substituted on a nitrogen atomforming part of the hetero ring. Specific examples of such heterocyclicamines include N-aminopropylmorpholine, N-aminoethylpiperazine, andN,N'-di-aminoethylpiperazine.

Also suitable as amines are the aminosulfonic acids and derivativesthereof corresponding to the formula: ##STR6## wherein R is OH, NH₂,ONH₄, etc.; R_(a) is a polyvalent organic group having a valence equalto x+y; R_(b) and R_(c) are each independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl with the proviso that at least one of R_(b) andR_(c) is hydrogen per aminosulfonic acid molecule; x and y are eachintegers equal to or greater than one. Each aminosulfonic reactant ischaracterized by at least one HN< or H₂ N-- group and at least one##STR7## group. These sulfonic acids can be aliphatic, cycloaliphatic oraromatic aminosulfonic acids and the corresponding functionalderivatives of the sulfo group. Specifically, the aminosulfonic acidscan be aromatic aminosulfonic acids, that is, where R_(a) is apolyvalent aromatic group such as phenylene where at least one ##STR8##group is attached directly to a nuclear carbon atom of the aromaticgroup. The aminosulfonic acid may also be a mono-amino aliphaticsulfonic acid; that is, an acid where x is one and R_(a) is a polyvalentaliphatic group such as ethylene, propylene, trimethylene, and2-methylene propylene. Other suitable aminosulfonic acids andderivatives thereof useful as amines in this invention are disclosed inU.S. Pat. Nos. 3,029,250; 3,367,864; and 3,926,820; which areincorporated herein by reference.

Hydrazine and substituted-hydrazine can also be used as amines in thisinvention. At least one of the nitrogens in the hydrazine must contain ahydrogen directly bonded thereto. The substituents which may be presenton the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and thelike. Usually, the substituents are alkyl, especially lower alkyl,phenyl, and substituted phenyl such as lower alkoxy-substituted phenylor lower alkyl-substituted phenyl. Specific examples of substitutedhydrazines are methylhydrazine, N,N-dimethylhydrazine,N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine,N-(para-tolyl)-N'-(n-butyl)-hydrazine, N-(para-nitrophenyl)-hydrazine,N-(para-nitrophenyl)-N-methylhydrazine,N,N'-di-(parachlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine,and the like.

The high molecular weight hydrocarbyl amines, both monoamines andpolyamines, which can be used as amines in this invention are generallyprepared by reacting a chlorinated polyolefin having a molecular weightof at least about 400 with ammonia or an amine. The amines that can beused are known in the art and described, for example, in U.S. Pat. Nos.3,275,554 and 3,438,757, both of which are incorporated herein byreference. These amines must possess at least one primary or secondaryamino group.

Another group of amines suitable for use in this invention are branchedpolyalkylene polyamines. The branched polyalkylene polyamines arepolyalkylene polyamines wherein the branched group is a side chaincontaining on the average at least one nitrogen-bonded aminoalkylene##STR9## group per nine amino units present on the main chain; forexample, 1-4 of such branched chains per nine units on the main chain,but preferably one side chain unit per nine main chain units. Thus,these polyamines contain at least three primary amino groups and atleast one tertiary amino group. These amines may be expressed by theformula: ##STR10## wherein R is an alkylene group such as ethylene,propylene, butylene and other homologs (both straight chained andbranched), etc., but preferably ethylene; and x, y and z are integers; xis in the range of from about 4 to about 24 or more, preferably fromabout 6 to about 18; y is in the range of from 1 to about 6 or more,preferably from 1 to about 3; and z is in the range of from zero toabout 6, preferably from zero to about 1. The x and y units may besequential, alternative, orderly or randomly distributed. A useful classof such polyamines includes those of the formula: ##STR11## wherein n isan integer in the range of from 1 to about 20 or more, preferably in therange of from 1 to about 3, and R is preferably ethylene, but may bepropylene, butylene, etc. (straight chained or branched). Usefulembodiments are represented by the formula: ##STR12## wherein n is aninteger in the range of 1 to about 3. The groups within the brackets maybe joined in a head-to-head or a head-to-tail fashion. U.S. Pat. Nos.3,200,106 and 3,259,578 are incorporated herein by reference for theirdisclosures relative to said polyamines.

Suitable amines also include polyoxyalkylene polyamines, e.g.,polyoxyalkylene diamines and polyoxyalkylene triamines, having averagemolecular weights ranging from about 200 to about 4000, preferably fromabout 400 to 2000. Examples of these polyoxyalkylene polyamines includethose amines represented by the formula:

    NH.sub.2 --Alkylene--O--Alkylene--.sub.m NH.sub.2

wherein m has a value of from about 3 to about 70, preferably from about10 to about 35; and the formula:

    R-[Alkylene--O--Alkylene--.sub.n NH.sub.2 ].sub.3-6

wherein n is a number in the range of from 1 to about 40, with theproviso that the sum of all of the n's is from about 3 to about 70 andgenerally from about 6 to about 35, and R is a polyvalent saturatedhydrocarbyl group of up to about 10 carbon atoms having a valence offrom about 3 to about 6. The alkylene groups may be straight or branchedchains and contain from 1 to about 7 carbon atoms, and usually from 1 toabout 4 carbon atoms. The various alkylene groups present within theabove formulae may be the same or different.

More specific examples of these polyamines include: ##STR13## wherein xhas a value of from about 3 to about 70, preferably from about 10 to 35;and ##STR14## wherein x+y+z have a total value ranging from about 3 toabout 30, preferably from about 5 to about 10.

Useful polyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to about 2000. Thepolyoxyalkylene polyamines are commercially available from the TexacoChemical Company, Inc. under the trade name "Jeffamine". U.S. Pat. Nos.3,804,763 and 3,948,800 are incorporated herein by reference for theirdisclosure of such polyoxyalkylene polyamines.

Useful amines are the alkylene polyamines, including the polyalkylenepolyamines, as described in more detail hereafter. The alkylenepolyamines include those conforming to the formula: ##STR15## wherein nis from 1 to about 10; each R is independently a hydrogen atom or ahydrocarbyl group or hydroxy-substituted hydrocarbyl group having up toabout 700 carbon atoms, preferably up to about 100 carbon atoms, morepreferably up to about 50 carbon atoms, more preferably up to about 30carbon atoms, and the "Alkylene" group has from about 1 to about 10carbon atoms with the preferred alkylene being ethylene or propylene.Useful are the alkylene polyamines wherein each R" is hydrogen with theethylene polyamines, and mixtures of ethylene polyamines beingparticularly preferred. Usually n will have an average value of fromabout 2 to about 7. Such alkylene polyamines include methylenepolyamines, ethylene polyamines, butylene polyamines, propylenepolyamines, pentylene polyamines, hexylene polyamines, heptylenepolyamines, etc. The higher homologs of such amines and relatedaminoalkyl-substituted piperazines are also included.

Alkylene polyamines that are useful include ethylene diamine,triethylene tetramine, propylene diamine, trimethylene diamine,hexamethylene diamine, decamethylene diamine, octamethylene diamine,di(heptamethylene) triamine, tripropylene tetramine, tetraethylenepentamine, trimethylene diamine, pentaethylene hexamine,di(trimethylene) triamine, N-(2-aminoethyl) piperazine,1,4-bis(2-aminoethyl) piperazine, and the like. Higher homologs as areobtained by condensing two or more of the above-illustrated alkyleneamines are useful as amines in this invention as are mixtures of two ormore of any of the afore-described polyamines.

Ethylene polyamines, such as those mentioned above, are described indetail under the heading "Diamines and Higher Amines" in TheEncyclopedia of Chemical Technology, Second Edition, Kirk and Othmer,Volume 7, pages 27-39, Interscience Publishers, Division of John Wileyand Sons, 1965, these pages being incorporated herein by reference. Suchcompounds are prepared most conveniently by the reaction of an alkylenechloride with ammonia or by reaction of an ethylene imine with aring-opening reagent such as ammonia, etc. These reactions result in theproduction of the somewhat complex mixtures of alkylene polyamines,including cyclic condensation products such as piperazines.

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkylsubstituents on the nitrogen atoms, are also useful in preparingcompositions of the present invention. Useful hydroxyalkyl-substitutedalkylene polyamines include those in which the hydroxyalkyl group is alower hydroxyalkyl group, i.e., having less than eight carbon atoms.Examples of such hydroxyalkyl-substituted polyamines includeN-(2-hydroxyethyl) ethylene ,diamine, N,N-bis(2-hydroxyethyl) ethylenediamine, 1-(2-hydroxyethyl)-piperazine, monohydroxypropyl-substituteddiethylene triamine, dihydroxypropyl-substituted tetraethylenepentamine, N-(3-hydroxybutyl) tetramethylene diamine, etc. Higherhomologs as are obtained by condensation of the above-illustratedhydroxy alkylene polyamines through amino groups or through hydroxygroups are likewise useful. Condensation through amino groups results ina higher amine accompanied by removal of ammonia and condensationthrough the hydroxy groups results in products containing ether linkagesaccompanied by removal of water.

Alkoxylated alkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine)can be used. Such polyamines can be made by reacting alkylene amines(e.g., ethylenediamine) with one or more alkylene oxides (e.g., ethyleneoxide, octadecene oxide) of two to about 20 carbons. Similar alkyleneoxide-alkanol amine reaction products can also be used such as theproducts made by reacting the afore-described primary, secondary ortertiary alkanol amines with ethylene, propylene or higher epoxides in a1:1 or 1:2 molar ratio. Reactant ratios and temperatures for carryingout such reactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl) ethylene diamine,N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl) piperazine,mono(hydroxypropyl)-substituted diethylene triamine,di(hydroxypropyl)-substituted tetraethylene pentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid polyamines arealso useful.

To prepare the carboxylic acid amide derivatives (A)(i), (B)(i)(a),(B)(ii)(a), (C)(i)(a) or (C)(ii)(a), the corresponding acid or anhydride(A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) or (C)(ii)(a), and ammonia orone or more of the above-described primary or secondary amines are mixedtogether and heated, optionally in the presence of a normally liquid,substantially inert organic liquid solvent/diluent, at temperatures inthe range of from about 50° C. to about 130° C., preferably from about80° C. to about 110° C. The acid or anhydride, and ammonia and/or amineare reacted in amounts sufficient to provide preferably up to about 0.95equivalent, more preferably from about 0.05 to about 0.95 equivalents ofammonia and/or amine per equivalent of the acid or anhydride. Forpurposes of this invention an equivalent of amine is that amount of theamine corresponding to the total weight of amine divided by the totalnumber of nitrogens present. Thus, octylamine has an equivalent weightequal to its molecular weight; ethylene diamine has an equivalent weightequal to one-half its molecular weight; and aminoethylpiperazine has anequivalent weight equal to one-third its molecular weight. Also, forexample, the equivalent weight of a commercially available mixture ofpolyalkylene polyamine can be determined by dividing the atomic weightof nitrogen (14) by the % N contained in the polyamine. Thus, apolyamine mixture having a % N of 34 would have an equivalent weight of41.2. An equivalent weight of ammonia is its molecular weight. Anequivalent of the acid or anhydride is the same as discussed above withrespect to reaction with alcohols.

Hydroxyamines Useful in Making Ester and/or Amide Derivatives (A)(i),(B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a)

Hydroxyamines, both mono- and polyamines, can be used in forming amideand/or ester derivatives (A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and(C)(ii)(a). Hydroxy-substituted amines having primary and/or secondaryamino groups are useful in making amide derivatives. Hydroxy-substitutedamines having only tertiary nitrogens are useful in making esterderivatives. The terms hydroxyamine, hydroxy-substituted amine andaminoalcohol describe the same class of compounds and are thusinterchangeable.

The hydroxyamines can be primary, secondary, or tertiary amines.Typically, the hydroxyamines are primary, secondary or tertiary alkanolamines or mixtures thereof. Such amines can be represented,respectfully, by the formulae: ##STR16## wherein each R is independentlya hydrocarbyl group of one to about eight carbon atoms orhydroxyl-substituted hydrocarbyl group of two to about eight carbonatoms and R' is a divalent hydrocarbyl group of about two to about 18carbon atoms. The group --R'--OH in such formulae represents thehydroxyl-substituted hydrocarbyl group. R' can be an acyclic, alicyclicor aromatic group. Typically, R' is an acyclic straight or branchedalkylene group such as an ethylene, 1,2-propylene, 1,2-butylene,1,2-octadecylene, etc. group. Where two R groups are present in the samemolecule they can be joined by a direct carbon-to-carbon bond or througha heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7-or8-membered ring structure. Examples of such heterocyclic amines includeN-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines,-oxazolidines, -thiazolidines and the like. Typically, however, each Ris a lower alkyl group of up to seven carbon atoms.

The hydroxyamines can also be an ether N-(hydroxy-substitutedhydrocarbyl)amine. These are hydroxyl-substituted poly(hydrocarbyloxy)analogs of the above-described hydroxy amines (these analogs alsoinclude hydroxyl-substituted oxyalkylene analogs). SuchN-(hydroxyl-substituted hydrocarbyl) amines can be conveniently preparedby reaction of epoxides with aforedescribed amines and can berepresented by the formulae: ##STR17## wherein x is a number from about2 to about 15 and R and R' are as described above.

Polyamine analogs of these hydroxy amines, particularly alkoxylatedalkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine) can also beused. Such polyamines can be made by reacting alkylene amines (e.g.,ethylenediamine) with one or more alkylene oxides (e.g., ethylene oxide,octadecene oxide) of two to about 20 carbons. Similar alkyleneoxide-alkanol amine reaction products can also be used such as theproducts made by reacting the afore-described primary, secondary ortertiary alkanol amines with ethylene, propylene or higher epoxides in a1:1 or 1:2 molar ratio. Reactant ratios and temperatures for carryingout such reactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl) ethylene diamine,N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl) piperazine,mono(hydroxypropyl)-substituted diethylene triamine,di(hydroxypropyl)-substituted tetraethylene pentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid mono- orpolyamines are also useful.

Examples of the N-(hydroxyl-substituted hydrocarbyl) amines includemono-, di-, and triethanol amine, diethylethanol amine, di-(3-hydroxylpropyl) amine, N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine,N,N-di-(2-hydroxyl propyl) amine, N-(2-hydroxyl ethyl) morpholine andits thio analog, N-(2-hydroxyl ethyl) cyclohexyl amine, N-3-hydroxylcyclopentyl amine, o-, m- and p-aminophenol, N-(hydroxyl ethyl)piperazine, N,N'-di(hydroxyl ethyl) piperazine, and the like.

Useful hydroxyamines include the hydroxy-substituted primary aminesdescribed in U.S. Pat. No. 3,576,743 by the general formula

    R.sub.a --NH.sub.2

wherein R_(a) is a monovalent organic group containing at least onealcoholic hydroxy group. The total number of carbon atoms in R_(a)preferably does not exceed about 20. Hydroxy-substituted aliphaticprimary amines containing a total of up to about 10 carbon atoms areuseful. The polyhydroxy-substituted alkanol primary amines wherein thereis only one amino group present (i.e., a primary amino group) having onealkyl substituent containing up to about 10 carbon atoms and up to about6 hydroxyl groups are useful. These alkanol primary amines correspond toR_(a) --NH₂ wherein R_(a) is a mono- or polyhydroxy-substituted alkylgroup. It is desirable that at least one of the hydroxyl groups be aprimary alcoholic hydroxyl group. Specific examples of thehydroxy-substituted primary amines include 2-amino-1-butanol,2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)-aniline,2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(beta-hydroxypropyl)-N'-(beta-aminoethyl)-piperazine,tris-(hydroxymethyl) amino methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine, beta-(beta-hydroxyethoxy)-ethyl amine, glucamine, glusoamine,4-amino-3-hydroxy-3-methyl-1-butene (which can be prepared according toprocedures known in the art by reacting isopreneoxide with ammonia),N-3-(aminopropyl)-4-( 2-hydroxyethyl)-piperadine,2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,N-(beta-hydroxyethyl)-1,3-diamino propane, 1,3-diamino-2-hydroxypropane,N-(beta-hydroxyethoxy-ethyl)-ethylenediamine, trismethylolaminomethaneand the like. U.S. Pat. No. 3,576,743 is incorporated herein byreference.

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkylsubstituents on the nitrogen atoms, are also useful. Usefulhydroxyalkyl-substituted alkylene polyamines include those in which thehydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less thaneight carbon atoms. Examples of such hydroxyalkyl-substituted polyaminesinclude N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)-piperazine,monohydroxypropyl-substituted diethylene triamine,dihydroxypropyl-substituted tetraethylene pentamine, N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as are obtained bycondensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia and condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater.

The carboxylic acid or anhydride can be reacted with a hydroxyamineaccording to conventional ester and/or amide-forming techniques. Thisnormally involves heating the acid or anhydride with the hydroxyamine,optionally in the presence of a normally liquid, substantially inert,organic liquid solvent/diluent. Temperatures of at least about 30° C. upto the decomposition temperature of the reaction component and/orproduct having the lowest such temperature can be used. This temperatureis preferably in the range of about 50° C. to about 130° C., preferablyabout 80° C. to about 100° C. when the carboxylic reactant is ananhydride. On the other hand, when the carboxylic reactant is an acid,this temperature is preferably in the range of about 100° C. up to about300° C. with temperatures in the range of about 125° C. to about 250° C.often being employed. Usually, up to about 0.95 equivalent, preferablyfrom about 0.05 to about 0.95 equivalent, more preferably about 0.5equivalent of hydroxyamine are used for each equivalent of acid oranhydride. For purposes of this reaction, an equivalent of ahydroxyamine is its molecular weight divided by the total number of--OH, >NH and --NH₂ groups present in the molecule. Thus,diethylethanolamine has an equivalent weight equal to its molecularweight; ethanolamine has an equivalent weight equal to one-half itsmolecular weight. An equivalent of acid or anhydride is the same asdiscussed above with respect to reaction with alcohols.

Components (A)(ii), (B)(i)(b) and (B)(ii)(b)

Components (A)(ii), (B)(i)(b) and (B)(ii)(b) include ammonia and all ofthe primary and secondary amines discussed above as being useful inpreparing the amide derivatives (A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a)and (C)(ii)(a), and the hydroxyamines discussed above as being useful inpreparing the amide and/or ester derivatives (A)(i), (B)(i)(a),(B)(ii)(a), (C)(i)(a) and (C)(ii)(a). In addition to ammonia and theamines and hydroxyamines discussed above, the amines (A)(ii), (B)(i)(b)and (B)(ii)(b) also include tertiary amines. The tertiary amines areanalogous to the primary and secondary amines and hydroxyaminesdiscussed above with the exception that hydrogen atoms in the H--N< or--NH₂ groups are replaced by hydrocarbyl groups. These tertiary aminescan be monoamines or polyamines. The monoamines are represented by theformula ##STR18## wherein R', R² and R³ are the same or differenthydrocarbyl groups. Preferably, R', R² and R³ are independentlyhydrocarbyl groups of from 1 to about 20 carbon atoms. The tertiaryamines can be symmetrical amines, dimethylalkyl amines or those derivedfrom the reaction of a primary amine or a secondary amine with ethyleneoxide. The tertiary amines can be aliphatic, cycloaliphatic, aromatic orheterocyclic, including aliphatic-substituted aromatic,aliphatic-substituted cycloaliphatic, aliphatic-substitutedheterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphaticsubstituted aromatic, cycloaliphatic-substituted heterocyclic,aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic,aromatic-substituted heterocyclic, heterocyclic-substituted aliphatic,heterocyclic-substituted cycloaliphatic and heterocyclic-substitutedaromatic amines. These tertiary amines may be saturated or unsaturated.If unsaturated, the amine is preferably free from acetylenicunsaturation (i.e., --C.tbd.C--). The tertiary amines may also containnon-hydrocarbon substituents or groups as long as these groups do notsignificantly interfere with the reaction of the amines with thecarboxylic acids and derivatives thereof of this invention. Suchnon-hydrocarbon substituents or groups include lower alkoxy, loweralkyl, mercapto, nitro, and interrupting groups such as --O-- and --S--(e.g., as in such groups as --CH₂ CH₂ --X--CH₂ CH₂ -- where X is --O--or --S--). Examples of such tertiary amines include trimethyl amine,triethyl amine, tripropyl amine, tributyl amine, monomethyldiethylamine, monoethyldimethyl amine, dimethylpropyl amine, dimethylbutylamine, dimethylpentyl amine, dimethylhexyl amine, dimethylheptyl amine,dimethyloctyl amine, dimethylnonyl amine, dimethyldecyl amine,dimethyldicodanyl amine, dimethylphenyl amine, N,N-dioctyl-1-octanamine,N,N-didodecyl-1-dodecanamine tricoco amine, trihydrogenated-tallowamine, N-methyldihydrogenated tallow amine, N,N-dimethyl-1-dodecanamine,N,N-dimethyl-1-tetradecanamine, N,N-dimethyl-1-hexadecanamine,N,N-dimethyl-1-octadecanamine, N,N-dimethylcocoamine,N,N-dimethylsoyaamine, N,N-dimethyl hydrogenated tallow amine, etc.

The alkali and alkaline earth metals that are useful as components(A)(ii), (B)(i)(b) and (B)(ii)(b) can be any alkali or alkaline earthmetal. The alkali metals are preferred. Sodium and potassium areparticularly preferred. Suitable metal bases include the free metals aswell as reactive compounds of such metals. The reactive compoundsinclude nitrates, nitrites, halides, carboxylates, phosphates,phosphites, sulfates, sulfites, carbonates, oxides, hydroxides,acetates, etc. Examples of such reactive compounds include sodium oxide,sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate,sodium pentylate, sodium phenoxide, potassium oxide, potassiumhydroxide, potassium carbonate, potassium methylate, potassiumpentylate, potassium phenoxide, lithium oxide, lithium hydroxide,lithium carbonate, lithium pentylate, calcium oxide, calcium hydroxide,calcium carbonate, calcium methylate, calcium ethylate, calciumpropylate, calcium chloride, calcium fluoride, calcium pentylate,calcium phenoxide, calcium nitrate, barium oxide, barium hydroxide,barium caronate, barium chloride, barium fluoride, barium methylate,barium propylate, barium pentylate, barium nitrate, magnesium oxide,magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesiumpropylate, magnesium chloride, magnesium bromide, barium iodide,magnesium phenoxide, etc. The above metal compounds are merelyillustrative of those useful in this invention and the invention is notto be considered as limited to such.

Reaction Between Components (A)(i), (B)(i)(a) and (B)(ii)(a) andCorresponding Components (A)(ii), (B)(i)(b) and (B)(ii)(b)

The carboxylic acid or anhydride, or ester or amide derivative (A)(i),(B)(i)(a) and (B)(ii)(a), and corresponding component (A)(ii), (B)(i)(b)and (B)(ii)(b) can be reacted together at a temperature ranging fromabout 30° C. to the decomposition temperature of the reaction componentsand/or products having the lowest such temperature. Preferably thereaction is carried out under salt-forming conditions using conventionaltechniques and the product thus formed comprises a salt moiety.Typically, the reactants are mixed together and heated to a temperaturein the range of about 50° C. to about 130° C., more preferably about 80°C. to about 110° C.; optionally, in the presence of a normally liquid,substantially inert organic liquid solvent/diluent, until the desiredproduct has formed. The ratio of reactants may be varied over a widerange. Generally, from about 0.1 to about 2 equivalents or more,preferably about 0.5 to about 1.5 equivalents of components (A)(ii),(B)(i)(b) and (B)(ii)(b) are used for each equivalent of thecorresponding component (A)(i), (B)(i)(a) or (B)(ii)(a).

For purposes of this reaction, an equivalent of component (A)(i),(B)(i)(a) or (B)(ii)(a) in the acid or anhydride form is the same asdiscussed above with respect to the reaction of the acids and anhydrideswith alcohols. The number of equivalents of component (A)(i), (B)(i)(a)and (B)(ii)(a) in the ester and/or amide derivative form, depends on thetotal number of carboxy groups present that are capable of reacting ascarboxylic acid acylating agents with the corresponding component(A)(ii), (B)(i)(b) or (B)(ii)(b); for example, the number of carboxygroups in (A)(i), (B)(i)(a) or (B)(ii)(a) that are capable of forming acarboxylic salt with the corresponding components (A)(ii), (B)(i)(b) and(B)(ii)(b). Thus, there would be one equivalent in an acid/amide derivedfrom one mole of a polyisobutylene-substituted succinic anhydride andone mole of ammonia. Similarly, there would be one equivalent in anacid/ester derived from one mole of a polyisobutylene-substitutedsuccinic anhydride and methanol. When components (A)(ii), (B)(i)(b) and(B)(ii)(b) are amines, an equivalent thereof is its molecular weightdivided by the total number of nitrogens present in the molecule thatare sufficiently basic to react with the corresponding component (A)(i),(B)(i)(a) and (B)(ii)(a). These include, for example, the nitrogen atomsof primary aliphatic amines, secondary aliphatic amines and tertiaryaliphatic amines as well as amines bearing one aryl group on thenitrogen atom (e.g., aniline). On the other hand, these do not include,for example, amides, (i.e., ##STR19## Thus, octylamine has an equivalentweight equal to its molecular weight; ethylene diamine has an equivalentweight equal to one-half of its molecular weight; both ethanolamine anddiethylethanolamine have equivalent weights equal to their molecularweights. The equivalent weight of a commercially available mixture ofpolyalkylene polyamines can be determined by dividing the atomic weightof nitrogen (14) by the % N contained in the polyamine; thus, apolyalkylene polyamine mixture having a % N of 34 would have anequivalent weight of 41.2. When component (A)(ii), (B)(i)(b) or(B)(ii)(b) is ammonia, an equivalent weight thereof is its molecularweight. When component (A)(ii), (B)(i)(b) or (B)(ii)(b) is an alkali oralkaline earth metal, an equivalent weight thereof is its atomic weightdivided by its valence.

In one embodiment of the invention, the product of the reaction betweencomponents (A)(i), (B)(i)(a) or (B)(ii)(a) and corresponding components(A)(ii), (B)(i)(b) or (B)(ii)(b) comprises a carboxylic salt moiety.Thus, this product is typically constituted of compositions containingat least one compound having at least one carboxylic salt linkage (i.e.,##STR20## wherein A⁺ is a metal, ammonium or amine cation) within itsmolecular structure. This product can also include other compounds suchas amides, esters, and the like. Preferably, these products containcompounds containing salt linkages in at least about 15% on a molarbasis of the carboxyl groups in such products, more preferably at leastabout 20%, more preferably at least about 35%, more preferably at leastabout 50%, more preferably at least about 75%, more preferably at leastabout 90%.

Components (C)(i)(b) and (C)(ii)(b)

Components (C)(i)(b) and (C)(ii)(b) can be the same or different, butpreferably are the same. Components (C)(i)(b) and (C)(ii)(b) can beammonia, or any of the amines or hydroxyamines discussed above as beinguseful in making the derivatives (A)(i), (B)(i)(a), (B)(ii)(a),(C)(i)(a) and (C)(ii)(a), or as being components (A)(ii), (B)(i)(b) or(B)(ii)(b). In addition to ammonia, and such amines and hydroxyamines,components (C)(i)(b) and (C)(ii)(b) can be any of the alkali oralkaline-earth metals or compounds thereof discussed above as beinguseful as components (A)(ii), (B)(i)(b) and (B)(ii)(b).

Component(C)(iii)

Component (C)(iii) can be any compound having (a) two or more primaryamino groups, (b) two or more secondary amino groups, (c) at least oneprimary amino group and at least one secondary amino group, (d) at leasttwo hydroxyl groups, or (e) at least one primary or secondary aminogroup and at least one hydroxyl group. These include polyamines, polyolsand hydroxyamines.

(1) Polyamines Useful as Component (C)(iii)

The polyamines useful as component (C)(iii) are characterized by thepresence within their structure of at least two --NH₂ groups, at leasttwo >NH groups, or at least one --NH₂ group and at least one >NH group.The polyamines discussed above as being useful in making the amidederivatives (A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a), orthe polyamines discussed above as being useful as components (A)(ii),(B)(i)(b) and (B)(ii)(b) that have the required number of --NH₂and/or >NH groups can be used as component (C)(iii).

These polyamines can be aliphatic, cycloaliphatic, aromatic orheterocyclic, including aliphatic-substituted aromatic,aliphatic-substituted cycloaliphatic, aliphatic-substitutedheterocyclic, cycloaliphatic-substituted aliphatic,cycloaliphatic-substituted aromatic, cycloaliphatic-substitutedheterocyclic, aromatic-substituted aliphatic, aromatic-substitutedcycloaliphatic, aromatic-substituted heterocyclic,heterocyclic-substituted aliphatic, heterocyclic-substitutedcycloaliphatic and heterocyclic-substituted aromatic amines. Theseamines may be saturated or unsaturated. If unsaturated, the amine ispreferably free from acetylenic unsaturation. These amines may alsocontain non-hydrocarbon substituents or groups as long as these groupsdo not interfere with the reaction of such amines with reactants (C)(i)and (C)(ii). Such non-hydrocarbon substituents or groups include loweralkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as--O-- and --S-- (e.g., as in such groups as

    --CH.sub.2 CH.sub.2 --X--CH.sub.2 CH.sub.2 --

where X is --O-- or --S--).

Useful polyamines are the alkylene polyamines. These alkylene polyaminescan be represented by the formula: ##STR21## wherein n is from 1 toabout 10, preferably from 1 to about 7; each R' and R" is independentlya hydrogen atom, a hydrocarbyl group or a hydroxy-substitutedhydrocarbyl group having up to about 700 carbon atoms, preferably up toabout 100 carbon atoms, more preferably up to about 50 carbon atoms,more preferably up to about 30 carbon atoms, with the proviso that atleast one of R' and at least one of R" are hydrogen; and the "Alkylene"group has from about 1 to about 10 carbon atoms, preferably from 1 toabout 4 carbon atoms, with the preferred Alkylene being ethylene orpropylene. Useful alkylene polyamines are those wherein each R' and eachR" are hydrogen with the ethylene polyamines, and mixtures of ethylenepolyamines being particularly preferred. Such alkylene polyaminesinclude methylene polyamines, ethylene polyamines, butylene polyamines,propylene polyamines, pentylene polyamines, hexylene polyamines,heptylene polyamines, etc. The higher homologs of such amines andrelated aminoalkyl-substituted piperazines are also included.

(2) Polyols Useful as Component (C)(iii)

The polyols useful as component (C)(iii) include the alcohols orpolyhydric alcohols with two or more hydroxyl groups discussed above asbeing useful in making the ester derivatives (A)(i), (B)(i)(a),(B)(ii)(a), (C)(i)(a) and (C)(ii)(a). These alcohols include polyols ofthe general formula:

    R.sub.1 (OH).sub.m

wherein R₁ is a monovalent or polyvalent organic group joined to the -OHgroups through carbon-to-oxygen bonds (that is, --COH wherein the carbonis not part of a carbonyl group) and m is an integer of from 2 to about10, preferably 2 to about 6. These alcohols can be aliphatic,cycloaliphatic, aromatic, and heterocyclic, includingaliphatic-substituted cycloaliphatic alcohols, aliphatic-substitutedaromatic alcohols, aliphatic-substituted heterocyclic alcohols,cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted heterocyclic alcohols,heterocyclic-substituted aliphatic alcohols, heterocyclic-substitutedcycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols.Except for the polyoxyalkylene alcohols, the polyhydric alcoholscorresponding to the formula R₁ (OH)_(m) preferably contain not morethan about 40 carbon atoms, more preferably not more than about 20carbon atoms. The alkylene glycols containing from 1 to about 20 carbonatoms, preferably 1 to about 10 carbon atoms, more preferably 1 to about6 carbon atoms, more preferably 1 to about 4 carbon atoms, andespecially ethylene glycol, are useful. The alcohols may containnon-hydrocarbon substituents or groups which do not interfere with thereaction of such alcohols with reactants (C)(i) and (C)(ii). Suchnon-hydrocarbon substituents or groups include lower alkoxy, loweralkyl, mercapto, nitro, and interrupting groups such as --O-- and --S--(e.g., as in such groups as --CH₂ CH₂ --X--CH₂ CH₂ where X is --O-- or--S--).

The polyhydric alcohols include polyhydroxy aromatic compounds.Polyhydric phenols and naphthols are useful hydroxyaromatic compounds.These hydroxy-substituted aromatic compounds may contain othersubstituents in addition to the hydroxy substituents such as halo,alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like. Usually, thehydroxy aromatic compound will contain from 2 to about 4 hydroxy groups.The aromatic hydroxy compounds are illustrated by the following specificexamples: resorcinol, catechol, p,p'-dihydroxy-biphenyl, hydroquinone,pyrogallol, phloroglucinol, hexylresorcinol, orcinol, etc.

(3) Hydroxyamines Useful as Component (C)(iii)

The hydroxyamines can be primary or secondary amines. They can also betertiary amines provided said tertiary amines also contain at least twohydroxyl groups. These hydroxyamines contain at least two >NH groups, atleast two --NH₂ groups, at least one --OH group and at least one >NH or--NH₂ group, or at least two --OH groups. The hydroxyamines having theforegoing characteristics that are discussed above as being useful inmaking the amide and/or ester derivatives (A)(i), (B)(i)(a), (B)(ii)(a),(C)(i)(a) or (C)(ii)(a), or as component (A)(ii), (B)(i)(b) or(B)(ii)(b) can be used as component (C)(iii).

The hydroxyamines include (a') N-(hydroxyl-substituted hydrocarbyl)primary or secondary amines, (b') hydroxyl-substitutedpoly(hydrocarbyloxy) analogs of (a'), or (c') mixtures of (a') and (b').These hydroxyamines include primary or secondary alkanol aminescontaining up to about 40 carbon atoms, preferably up to about 20 carbonatoms, more preferably up to about 10 carbon atoms. Useful hydroxyaminesinclude the primary and secondary alkanol amines represented,respectfully, by the formulae: ##STR22## wherein R is a hydrocarbylgroup of 1 to about 8 carbon atoms or hydroxyl-substituted hydrocarbylgroup of 2 to about 8 carbon atoms and R' is a divalent hydrocarbylgroup of about 2 to about 18 carbon atoms. The group --R'--OH in suchformulae represents the hydroxyl-substituted hydrocarbyl group. R' canbe an acyclic, alicyclic or aromatic group. Typically, R' is an acyclicstraight or branched alkylene group such as an ethylene, 1,2-propylene,1,2-butylene, 1,2-octadecylene, etc. group. Typically, R is a loweralkyl group of up to seven carbon atoms.

The hydroxyamines can also be ether N-(hydroxy-substitutedhydrocarbyl)amines. These are hydroxyl-substituted poly(hydrocarbyloxy)analogs of the above-described primary and secondary alkanol amines(these analogs also include hydroxyl-substituted oxyalkylene analogs).Such N-(hydroxyl-substituted hydrocarbyl) amines can be convenientlyprepared by reaction of epoxides with afore-described amines and can berepresented by the formulae: ##STR23## wherein x is a number from about2 to about 15 and R and R' are as described above.

Reaction of Components (C)(i) and (C)(ii) with Component (C)(iii) toForm Component (C)

Components (C)(i)(a) and (C)(ii)(a) can be reacted with component(C)(iii) to form an intermediate. The intermediate is then reacted withcomponents (C)(i)(b) and (C)(ii)(b) to form component (C). Analternative method of preparing component (C) involves reactingcomponents (C)(i)(a) and (C)(i)(b) with each other to form a firstintermediate, separately reacting components (C)(ii)(a) and (C)(ii)(b)with each other to form a second intermediate, then reacting a mixtureof these two intermediates with component (C)(iii) to form component(C).

The ratio of reactants utilized in the preparation of component (C) maybe varied over a wide range. Generally, for each equivalent of each ofcomponents agents (C)(i)(a) and (C)(ii)(a), at least about oneequivalent of component (C)(iii) is used. From about 0.1 to about 2equivalents or more of components (C)(ii)(a) and (C)(ii)(b) are used foreach equivalent of components (C)(i)(a) and (C)(ii)(a), respectively.The upper limit of component (C)(iii) is about 2 equivalents ofcomponent (C)(iii) for each equivalent of component (C)(i)(a), and abouttwo equivalents of component (C)(iii) for each equivalent of component(C)(ii)(a). Generally the ratio of equivalents of components (C)(i)(a)to (C)(ii)(a) is about 0.5 to about 2, with about 1:1 being preferred.Preferred amounts of the reactants are about 2 equivalents of thecomponent (C)(iii) and from about 0.1 to about 2 equivalents of each ofcomponents (C)(i)(b) and (C)(ii)(b) for each equivalent of each ofcomponents (C)(i)(a) and (C)(ii)(a).

The number of equivalents of components (C)(i)(a) and (C)(ii)(a) dependson the total number of carboxylic functions present in each. Indetermining the number of equivalents for each of the components(C)(i)(a) and (C)(ii)(a), those carboxyl functions which are not capableof reacting as a carboxylic acid acylating agent are excluded. Ingeneral, however, there is one equivalent of component (C)(i)(a) and(C)(ii)(a) for each carboxy group. For example, there would be twoequivalents in an anhydride derived from the reaction of one mole ofolefin polymer and one mole of maleic anhydride.

An equivalent weight of a polyamine is the molecular weight of thepolyamine divided by the total number of nitrogens present in themolecule. If the polyamine is to be used as component (C)(iii), tertiaryamino groups are not counted. On the other hand, if the polyamine is tobe used as component (C)(i)(b) or (C)(ii)(b), tertiary amino groups arecounted. Thus, ethylene diamine has an equivalent weight equal toone-half of its molecular weight; diethylene triamine has an equivalentweight equal to one-third its molecular weight. The equivalent weight ofa commercially available mixture of polyalkylene polyamine can hedetermined by dividing the atomic weight of nitrogen (14) by the % Ncontained in the polyamine; thus, a polyamine mixture having a % N of 34would have an equivalent weight of 41.2. An equivalent weight of ammoniaor a monoamine is its molecular weight.

An equivalent weight of polyhydric alcohol is its molecular weightdivided by the total number of hydroxyl groups present in the molecule.Thus, an equivalent weight of ethylene glycol is one-half its molecularweight.

An equivalent weight of a hydroxyamine which is to be used as component(C)(iii) is its molecular weight divided by the total number of--OH, >NH and --NH₂ groups present in the molecule. Thus,dimethylethanolamine when used as component (C)(iii) has an equivalentweight equal to its molecular weight; ethanolamine has an equivalentweight equal to one-half its molecular weight. On the other hand, if thehydroxyamine is to be used as components (C)(i)(b) or (C)(ii)(b), anequivalent weight thereof would be its molecular weight divided by thetotal number of nitrogen groups present in the molecule. Thus,dimethylethanolamine, when used as component (C)(i)(b) or (C)(ii)(b),would have an equivalent weight equal to its molecular weight;ethanolamine would also have an equivalent weight equal to its molecularweight.

An equivalent weight of an alkali or alkaline earth metal is its atomicweight divided by its valence.

Components (C)(i)(a) and (C)(ii)(a) can be reacted with component(C)(iii) according to conventional ester- and/or amide-formingtechniques. This normally involves heating components (C)(i)(a) and(C)(ii)(a) with component (C)(iii), optionally in the presence of anormally liquid, substantially inert, organic liquid solvent/diluent.Temperatures of at least about 30° C. up to the decompositiontemperature of the reaction component and/or product having the lowestsuch temperature can be used. This temperature is preferably in therange of about 50° C. to about 130° C., more preferably about 80° C. toabout 100° C. when components (C)(i)(a) and (C)(ii)(a) are anhydrides.On the other hand, when components (C)(i)(a) and (C)(ii)(a) are acids,this temperature is preferably in the range of about 100° C. to about300° C. with temperatures in the range of about 125° C. to about 250° C.often being employed.

The reactions between components (C)(i)(a) and (C)(ii)(a), and (C)(i)(b)and (C)(ii)(b) are preferably carried out under salt forming conditionsusing conventional techniques. Typically, components (C)(i)(a) and(C)(ii)(a), and (C)(i)(b) and (C)(ii)(b) are mixed together and heatedto a temperature in the range of about 20° C. up to the decompositiontemperature of the reaction component and/or product having the lowestsuch temperature, preferably about 50° C. to about 130° C., morepreferably about 80° C. to about 110° C.; optionally, in the presence ofa normally liquid, substantially inert organic liquid solvent/diluent,until the desired product has formed.

The product of the reaction between components (C)(i)(a) and (C)(ii)(a),and (C)(i)(b) and (C)(ii)(b), respectively, preferably contain at leastsome salt linkage. Preferably at least about 10% on a molar basis, morepreferably at least about 30%, more preferably at least about 50%, morepreferably at least about 70%, and advantageously up to about 100% ofthe carboxyl groups in components (C)(ii)(a) and (C)(ii)(b) that reactwith components (C)(i)(a) and (C)(i)(b), respectively, form a saltlinkage.

Component (II)

The phosphorus-containing acids (II)(A') are represented by the formula##STR24## wherein X¹, X², X³ and X⁴ are independently oxygen or sulfur;a and b are in dependently zero or one, and R¹ and R² are independentlyhydrocarbyl groups. Illustrative examples of usefulphosphorus-containing acids include

1. Dihydrocarbyl phosphinodithioic acids corresponding to the formula##STR25##

2. S-hydrocarbyl hydrocarbyl phosphonotrithioic acids corresponding tothe formula ##STR26##

3. O-hydrocarbyl hydrocarbyl phosphonodithioic acids corresponding tothe formula ##STR27##

4. S,S'-dihydrocarbyl phosphorotetrathioic acids corresponding to theformula ##STR28##

5. O,S-dihydrocarbyl phosphorotrithioic acids corresponding to theformula ##STR29##

6. O,O'-dihydrocarbyl phosphorodithioic acids corresponding to theformula ##STR30##

Preferred acids of the formula ##STR31## are readily obtainable by thereaction of phosphorus pentasulfide (P₂ S₅) and an alcohol or a phenol.The reaction involves mixing at a temperature of about 20° C. to about200° C., four moles of alcohol or a phenol with one mole of phosphoruspentasulfide. Hydrogen sulfide is liberated in this reaction. Theoxygen-containing analogs of these acids are conveniently prepared bytreating the dithioic acid with water or steam which, in effect,replaces one or both of the sulfur atoms.

Preferred phosphorus-containing acids (II)(A') are phosphorus- andsulfur-containing acids. These preferred acids preferably include thoseacids wherein at least one X³ or X⁴ is sulfur, and more preferably bothX³ and X⁴ are sulfur, at least one X¹ or X² is oxygen, more preferablyboth X¹ and X² are oxygen, and a and b are each 1. Mixtures of theseacids may be employed in accordance with this invention.

R¹ and R² are independently hydrocarbyl groups that are preferably freefrom acetylenic unsaturation and usually also free from ethylenicunsaturation and preferably have from about 1 to about 50 carbon atoms,more preferably from about 1 to about 30 carbon atoms, more preferablyfrom about 3 to about 18 carbon atoms, more preferably from about 4 toabout 12 carbon atoms, more preferably from about 4 to about 8 carbonatoms. Each R¹ and R² can be the same as the other, although they may bedifferent and either or both may be mixtures. Examples of preferred R¹and R² groups include t-butyl, isobutyl, amyl, isooctyl, decyl, dodecyl,eicosyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl,alkylnaphthyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl,alkylnaphthylalkyl, and the like.

The metals that are useful in making the salts (II)(B') are those thatform salts with the phosphorus-containing acids (II)(A'), and formmetal-containing complexes when the salts (II)(B') are reacted withcomponent (I). These metals include magnesium, calcium, strontium,chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver,zinc, cadmium, aluminum, tin, lead, or a mixture of two or more thereof.Calcium, zinc, cadmium, copper, nickel or a mixture of two or morethereof are preferred. Zinc and copper are more preferred. Zinc is morepreferred.

Suitable metal bases for the preparations of the metal salts (II)(B')include the free metals previously enumerated and their nitrates,nitrites, halides, carboxylates, phosphates, phosphites, sulfates,sulfites, carbonates, oxides, hydroxides, acetates, etc. Examplesinclude magnesium oxide, magnesium hydroxide, calcium hydroxide, calciumacetate, lead oxide, cobaltous nitrate, cobaltous oxide, cobaltic oxide,cobaltic nitrite, cobaltic phosphate, cobaltous chloride, cobalticchloride, cobaltous carbonate, chromous acetate, chromic acetate,chromic bromide, chromous chloride,, chromic fluoride, chromous oxide,chromium dioxide, chromic oxide, chromic sulfite, chromous sulfateheptahydrate, chromic sulfate, chromic formate, chromic hexanoate,chromium oxychloride, chromic phosphite, manganous acetate, manganousbenzoate, manganous carbonate, manganese dichloride, manganesetrichloride, manganous citrate, manganous formate, manganous nitrate,manganous oxalate, manganese monooxide, manganese dioxide, manganesetrioxide, manganese heptoxide, manganic phosphate, manganouspyrophosphate, manganic metaphosphate, manganous hypophosphite,manganous valerate, ferrous acetate, ferric benzoate, ferrous bromide,ferrous carbonate, ferric formate, ferrous lactate, ferrous nitrate,ferrous oxide, ferric oxide, ferric hypophosphite, ferric sulfate,ferrous sulfite, ferric hydrosulfite, nickel dibromide, nickeldichloride, nickel sulfite, cupric propionate, cupric acetate, cupricmetaborate, cupric benzoate, cupric formate, cupric laurate, cupricnitrite; cupric oxychloride, cupric palmitate, cupric salicylate, zincacetate, zinc benzoate, zinc borate, zinc bromide, zinc chromate, zincdichromate, zinc iodide, zinc lactate, zinc nitrate, zinc oxide, zincstearate, zinc sulfite, cadmium benzoate, cadmium carbonate, cadmiumbutyrate, cadmium chloroacetate, cadmium fumerate, cadmium nitrate,cadmium di-hydrogen-phosphate, cadmium sulfite, cadmium oxide, etc.Hydrates of the above compounds are useful.

The metal salts (II)(B') can be acidic, neutral or overbased. The term"neutral salt" refers to salts characterized by metal content equal tothat which would be present according to the stoichiometry of the metaland the phosphorus-containing acid (II)(A') reacted with the metal.Thus, if a phosphorodithioic acid, ##STR32## is neutralized with a basicmetal compound, e.g., zinc oxide, the neutral metal salt produced wouldcontain one equivalent of zinc for each equivalent of acid, i.e.,##STR33## For purposes of this reaction, an equivalent weight ofphosphorus-containing acid (II)(A') is its molecular weight divided bythe number of --PXXH groups therein. The equivalent of a metal for thispurpose is its atomic weight divided by its valence. With the presentinvention, component (II)(B') can contain more or less than thestoichiometric amount of metal. The products containing less than thestoichiometric amount of metal are acidic materials. The productscontaining more than the stoichiometric amount of metal are overbasedmaterials. For example, salts of component (II)(B') containing 50% ofthe metal present in the corresponding neutral salt are acidic, whilesalts of component (II)(B') containing 200% of the metal present in thecorresponding neutral salt are overbased. Component (II)(B') has up toabout 200%, preferably about 50% to about 200%, more preferably about80% to about 150%, more preferably about 90% to about 135%, morepreferably about 90% to about 110% of the metal present in thecorresponding neutral salt.

The temperature at which the salts (II)(B') are prepared is generallybetween about 30° C. and about 150° C., preferably between about 30° C.and about 125° C. It is preferred to employ temperatures in the range ofabout 50° C. to about 125° C., more preferably about 75° C. to about125° C. The pressure is preferably atmospheric pressure. The reactioncan be conducted in the presence of a substantially inert, normallyliquid organic diluent such as naphtha, benzene, xylene, mineral oil orthe like.

Reaction Between Components (I) and (II):

The inventive compositions are prepared by reacting component (I) withcomponent (II). Component (I) can be prepared separately and then laterreacted with component (II), or component (I) can be initially preparedand then immediately or shortly thereafter reacted with component (II)in the same reaction vessel.

To prepare the inventive compositions, one or more of component (I) andone or more of component (II) are mixed together, optionally in thepresence of a normally liquid substantially inert organicsolvent/diluent at a temperature in the range of about 30° C. up to thedecomposition temperature of the reaction components and/or productshaving the lowest such temperature. Preferably, the reactants are mixedtogether and heated to a temperature in the range of about 30° C. toabout 100° C., more preferably about 60° C. to about 95° C., morepreferably about 70° C. to about 90° C., more preferably about 75° C. toabout 85° C., until the desired product is formed. In one embodiment,the reactants are mixed and heated for about 15 minutes to about 5hours, preferably about 1 to about 3 hours. The weight ratio ofcomponent (I) to component (II) is preferably from about 95:5 to about50:50, more preferably about 95:5 to about 70:30, more preferably about95:5 to about 80:20, more preferably about 95:5 to about 85:15.

In one embodiment of the invention, component (II) is (II)(B') and thereaction product formed by the reaction of component (I) with component(II)(B') is a metal-containing complex. While not wishing to be bound bytheory, it is believed that in the formation of such complexes thenitrogen in component (I) complexes with the metal in component (II).

Examples 1-19 are illustrative of the preparation of component (I) ofthe invention. Examples 20-33 are illustrative of the preparation of theinventive compositions derived from components (I) and (II). Unlessotherwise indicated, in the following examples as well as throughout theentire specification and in the appended claims, all parts andpercentages are by weight, all temperatures are in degrees centigrade,and all pressures are atmospheric.

EXAMPLE 1

2240 parts of polyisobutenyl (number average molecular weight of about950 and weight average molecular weight of about 2100) substitutedsuccinic anhydride are heated to a temperature of about 90° C. 468 partsof diethylethanolamine are added over a 2-hour period. The mixture isheated for an additional hour at 90° to provide the desired product.

EXAMPLE 2

1120 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 and 325 parts of a hydrocarbyl-substituted succinic anhydridederived from one mole of a C₁₆ alpha-olefin and one mole of maleicanhydride are heated to a temperature of 93° C. with stirring andmaintained at that temperature for one hour. 62 parts of ethylene glycolare added to the mixture. The mixture is maintained at a temperature of93°-105° C. for 2 hours. 178 parts of dimethylethanolamine are added tothe mixture over a period of 0.5 hour. The mixture is maintained at93°-104° C. for 2.5 hours then cooled to 70° C. to provide the desiredproduct.

EXAMPLE 3

2228 parts of polyisobutenyl-substituted succinic anhydride used inExample 1 are heated to 90° C. with stirring. 178 parts ofdimethylethanolamine are added over a period of one hour whilemaintaining the temperature at 90°-97° C. The mixture is maintained at90°-97° C. for an additional 0.5 hour to provide the desired product.

EXAMPLE 4

1600 parts of hydrocarbyl-substituted succinic anhydride derived from aC₁₆ alpha-olefin and maleic anhydride are heated to 80°-90° C. 445 partsof dimethylethanolamine are added over a period of one hour whilemaintaining the temperature at 85°-95° C. The mixture is maintained at85°-95° C. for an additional one hour, and then cooled to 60° C. toprovide the desired product.

EXAMPLE 5

2240 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 are heated to a temperature in the range of 110°-116° C. 174parts of morpholine are then added dropwise to the anhydride. Aftercompletion of the addition of morpholine, the resulting mixture ismaintained at a temperature of 116°-126° C. for two hours. 234 parts ofdiethylethanolamine are then added dropwise while the temperature ismaintained at 116°-126° C. After completion of the addition of diethylethanolamine, the resulting mixture is maintained at 116°-126° C. for50 minutes with stirring.

EXAMPLE 6

A mixture of 1100 parts of the polyisobutenyl-substituted succinicanhydride used in Example 1 and 100 parts of Carbowax 200 (a product ofUnion Carbide identified as a polyethylene glycol having a molecularweight of 200) are heated to a temperature of 123°-134° C., maintainedat said temperature for 2 hours, then cooled to 100° C. 117 parts ofdiethylethanolamine are added to the resulting product over a 0.2 hourperiod while maintaining the temperature at 100° C. The mixture is thencooled to room temperature.

EXAMPLE 7

A mixture of 1100 parts of the polyisobutenyl-substituted succinicanhydride used in Example 1 and 34 parts of pentaerythritol are heatedto a temperature of 125°-160° C., maintained at said temperature for 4hours, then adjusted to 130° C. 117 parts of diethylethanolamine areadded to the mixture. The temperature is maintained at 100°-130° C. for1 hour. The resulting product is then cooled to room temperature.

EXAMPLE 8

A mixture of 2240 parts of the polyisobutenyl-substituted succinicanhydride used in Example 1 and 300 parts of a 40 SUS mineral seal oilare heated to 50° C. with continuous stirring over a 0.5-hour period. 54parts of tap water are added and the resulting mixture is heated from50° C. to 92° C. over a 0.5-hour period, then maintained at 92°-98° C.for 5 hours. 244 parts of monoethanolamine are added and the resultingmixture is maintained at 92°-98° C., then cooled to room temperature.

EXAMPLE 9

A mixture of 2240 parts of the polyisobutenyl-substituted succinicanhydride used in Example 1 and 62 parts of ethylene glycol are heatedto a temperature in the range of 116°-120° C., then maintained at saidtemperature for 5 hours. The temperature of the mixture is thenincreased to a temperature in the range of 138°-146° C. and maintainedat said increased temperature for an additional 4.5 hours. Thetemperature of the mixture is then decreased to 115° C. over a period of0.5 hour. 122 parts of monoethanolamine are added to the mixture over aperiod of 0.5 hour while maintaining the temperature at 115°-120° C. Themixture is then stirred for an additional 0.5 hour while maintaining thetemperature at 15°-120° C., then cooled to room temperature.

EXAMPLE 10

2895 parts of polyisobutenyl (number average molecular weight of 1700)substituted succinic anhydride are heated to 121° C. over a 1-hourperiod. 605 parts of diethylethanolamine are added over a 2-hour periodwhile maintaining the temperature of the mixture at 121°-128° C.

The mixture is maintained at 121°-123° C. for an additional hour, andthen cooled to 50° C. to provide the desired product.

EXAMPLE 11

A mixture of 1000 parts of the polyisobutenyl-substituted succinicanhydride used in Example 1 and 337 parts of a blend oil are heated to85° C. 26 parts of tap water are added to the mixture. The mixture isheated to 102° C. over a period of 0.25 hour. The mixture is maintainedat a temperature of 102°-105° C. for 4 hours, and then cooled to 70° C.209 parts of diethylethanolamine are added to the mixture over a0.2-hour period, and the mixture exotherms to 79° C. The mixture is thenmaintained at a temperature of 78°-79° C. for 1.5 hours and then cooledto room temperature to provide the desired product.

EXAMPLE 12

1120 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 are heated to 85°-90° C. over a 1-hour period. 117 parts ofdiethylethanolamine are added over a 0.5-hour period. The resultingmixture is maintained at a temperature of 85°-90° C. for 4 hours, thencooled to room temperature to provide the desired product.

EXAMPLE 13

A mixture of 917 parts of diluent oil, 40 parts of diatomaceous earthfilter aid, 10 parts of caustic soda, 0.2 part of a silicone-basedanti-foam agent, 135 parts of 3-amino-1,2,4-triazole, and 6.67 parts ofa commercial polyethylene polyamine mixture containing 33.5% nitrogenand substantially corresponding to tetraethylene pentamine are heated toa temperature of 121° C. with stirring. 1000 parts of thepolyisobutylene-substituted succinic anhydride used in Example 1 areslowly added to the mixture over a period of about one hour, and duringsuch addition the temperature of the mixture is increased from 121° C.to 154° C. The mixture is then maintained at a temperature of 154°-160°C. with nitrogen blowing for 12 hours. The mixture is then cooled to138°-149° C. and filtered. A final oil adjustment is made to adjust theproduct to a 45% by weight diluent oil.

EXAMPLE 14

6720 parts of the polyisobutenyl succinic anhydride used in Example 1are heated to 90° C. with stirring. 702 parts of diethylethanolamine areadded over a 1.5-hour period. This intermediate mixture is then heatedfor an additional 0.5 hour at 90° C. Then 366 parts of monoethanolamineare slowly added. The mixture is maintained at 90° C. for 0.5 hour andthen cooled to provide the desired product.

EXAMPLE 15

A mixture of 2644 parts of the polyisobutenyl succinic anhydride used inExample 1 and 75 parts of ethylene glycol are heated to a temperature of120° C., and maintained at said temperature for 4 hours. The temperatureof the mixture is then increased to 160°-170° C., maintained at saidtemperature for 2 hours, then reduced to 120° C. 281 parts ofdiethylethanolamine are added to the mixture over a 0.25 hour period.The temperature of the mixture is maintained at 115°-120° C. for 1 hour.The mixture is then cooled to room temperature to provide the desiredproduct.

EXAMPLE 16

A mixture of 2240 parts of the polyisobutylene-substituted succinicanhydride used in Example 1 and 86 parts of piperazine are heated to atemperature of 116°-126° C. and maintained at said temperature for 2hours. 234 parts of diethylethanolamine are added dropwise to themixture. The temperature is maintained at 116°-126° C. for 50 minutes.The resulting product is then cooled to room temperature.

EXAMPLE 17

One mole of the polyisobutenyl-substituted succinic anhydride used inExample 1 and one mole of piperidene are heated at a temperature of105°-120° C. for 3 hours to provide the desired product.

EXAMPLE 18

One mole of the polyisobutenyl-substituted succinic anhydride used inExample 1 and two moles of morpholine are heated at a temperature of94°-105° C. for 2.5 hours to provide the desired product.

EXAMPLE 19

One mole of the polyisobutenyl-substituted succinic anhydride used inExample 1 and two moles of ethanolamine are heated at a temperature of85°-95° C. for 1 hour to provide the desired product.

EXAMPLE 20

4800 parts of the product from Example 1, and 2640 parts of 40N oil areheated to 80° C. with continuous stirring. 536 parts of neutral zincsalt of O,O'-di(isooctyl) phosphorodithioic acid are added to themixture. The mixture is heated at 80°-84° C. for 1 hour. 24 parts ofwater are added to the mixture and blended for 20 minutes to provide thedesired product. Infrared analysis indicates the formation of a complex.This is shown by a shift in the P=S absorption in the IR from 660 cm⁻¹to 670-680 cm³¹ 1 with the reaction product.

EXAMPLE 21

989.2 parts of the poly isobutenyl-substituted succinic anhydride usedin Example 1 and 663.4 parts of 40N oil are heated to 90°-95° C. withcontinuous stirring. 208.0 parts of diethylethanolamine are added over a2-hour period with continuous stirring while maintaining the temperatureat 90°-95° C. The resulting mixture is heated for an additional 4.5hours at 90°-95° C. 133.4 parts of neutral zinc salt ofO,O'-di(isooctyl) phosphorodithioic acid are added over 0.5 hour whilemaintaining the mixture at 90°-95° C. 6.0 parts of water are added. Theresulting mixture is maintained at 90°-95° C. for 1.5 hours, then cooledto room temperature to provide the desired product.

EXAMPLE 22

989.2 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 and 663.4 parts of 40N oil are heated to 90°-95° C. withcontinuous stirring. 208.0 parts of diethylethanolamine are added over a2-hour period with continuous stirring while maintaining the temperatureat 90°-95° C. The resulting mixture is heated for an additional 4.5hours at 90°-95° C. The mixture is cooled to 80° C. 133.4 parts ofneutral zinc salt of O,O'-di(isooctyl) phosphorodithioic acid are addedover 0.5 hour while maintaining the mixture at 80° C. 6.0 parts of waterare added. The resulting mixture is maintained at 80° C. for 1.5 hours,then cooled to room temperature to provide the desired product.

EXAMPLE 23

989.2 parts of the poly isobutenyl-substituted succinic anhydride usedin Example 1 are heated with continuous stirring to 90°-95° C. 208.0parts of diethylethanolamine are added over a 2-hour period withcontinuous stirring while maintaining the temperature at 90°-95° C. Theresulting mixture is heated for an additional 4.5 hours at 90°-95° C.663.4 parts of 40N oil are added over a 15-minute period whilemaintaining the temperature at 90°-95° C. 133.4 parts of neutral zincsalt of O,O'-di(isooctyl) phosphorodithioic acid are added over 0.5 hourwhile maintaining the mixture at 90°-95° C. 6.0 parts of water areadded. The resulting mixture is maintained at 90°-95° C. for 1.5 hours,then cooled to room temperature to provide the desired product.

EXAMPLE 24

989.2 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 are heated to 90°-95° C. with continuous stirring. 208.0 partsof diethylethanolamine are added over a 2-hour period with continuousstirring while maintaining the temperature at 90°-95° C. The resultingmixture is heated for an additional 4.5 hours at 90°-95° C. 663.4 partsof 40N oil are added. The mixture is cooled to 80° C. 133.4 parts ofneutral zinc salt of O,O'-di(isooctyl) phosphorodithioic acid are addedover 0.5 hour while maintaining the mixture at 79°-82° C. 6.0 parts ofwater are added. The resulting mixture is maintained at 79°-82° C. for1.5 hours, then cooled to room temperature to provide the desiredproduct.

EXAMPLE 25

989.2 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 are heated to 90°-95° C. with continuous stirring. 208.0 partsof diethylethanolamine are added over a 2-hour period with continuousstirring while maintaining the temperature at 90°-95° C. The resultingmixture is heated for an additional 4.5 hours at 90°-95° C. The mixtureis cooled to 80° C. 133.4 parts of neutral zinc salt ofO,O'-di(isooctyl) phosphorodithioic acid are added over 0.5 hour whilemaintaining the mixture at 80° C. 6.0 parts of water are added. Theresulting mixture is maintained at 79°-82° C. for 1.5 hours. 663.4 partsof 40N oil are added. The mixture is stirred for 30 minutes whilecooling to 60° C. to provide the desired product.

EXAMPLE 26

989.2 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 and 663.4 parts of 40N oil are heated to 90°-95° C. withcontinuous stirring. 208.0 parts of diethylethanolamine are added over a2-hour period with continuous stirring while maintaining the temperatureat 90°-95° C. The resulting mixture is heated for an additional 4.5hours at 90°-95° C. The mixture is cooled to 81° C. 133.4 parts ofneutral zinc salt of O,O'-di(isooctyl) phosphorodithioic acid are addedover 0.5 hour. 6.0 parts of water are added. The resulting mixture ismaintained at 79°-82° C. for 1.5 hours with stirring, then cooled toroom temperature to provide the desired product.

EXAMPLE 27

900 parts of the product from Example 1, are heated to 80°-90° C. withcontinuous stirring. 100 parts of neutral zinc salt of O,O'-di(isooctyl)phosphorodithioic acid are added over a 20-minute period whilemaintaining the temperature at 80°-90° C. The mixture is maintained at80°-90° C. for 2 hours then cooled to room temperature to provide thedesired product.

EXAMPLE 28

1120 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 are heated to 101°- 107° C. with continuous stirring. 234parts of diethylethanolamine are added over a 30-40 minute period withcontinuous stirring while maintaining the temperature at 104°-110° C.The resulting mixture is heated for an additional 3 hours at 104° C. Themixture is cooled to 75°-80° C. 150.5 parts of neutral zinc salt ofO,O'-di(isooctyl) phosphorodithioic acid are added over a 15-20 minuteperiod while maintaining the mixture at 75°-80° C. The resulting mixtureis maintained at 75°-80° C. for 2 hours, then cooled to room temperatureto provide the desired product.

EXAMPLE 29

450 parts of the product of Example 2 and 50 parts of neutral zinc saltof O,O'di(isooctyl) phosphorodithioic acid are heated at a temperatureof 80° C. for 2 hours with stirring, then cooled to room temperature toprovide the desired product.

EXAMPLE 30

360 parts of the product of Example 3 and 40 parts of neutral zinc saltof O,O'di(isooctyl) phosphorodithioic acid are heated at a temperatureof 80° C. for 2 hours with stirring, then cooled to room temperature toprovide the desired product.

EXAMPLE 31

450 parts of the product of Example 4 and 50 parts of neutral zinc saltof O,O'-di(isooctyl) phosphorodithioic acid are heated at a temperatureof 80° C. for 2 hours with stirring, then cooled to room temperature toprovide the desired product.

EXAMPLE 32

90 parts of the reaction product of one mole of thepolyisobutenyl-substituted succinic anhydride used in Example 1 with 1.5moles of diethanolamine, and 10 parts of neutral zinc salt ofO,O'-di(isooctyl) phosphorodithioic acid are heated at a temperature of80° C. for 2 hours then cooled to room temperature to provide thedesired product.

EXAMPLE 33

900 parts of the product of Example 2 are heated to 80°-90° C. withstirring. 100 parts of neutral zinc salt of O,O'-di(isooctyl)phosphorodithioic acid are added over a 20-minute period with stirringwhile maintaining the temperature at 80°-90° C. The mixture ismaintained at 80°-90° C. for 1.25 hours with stirring, then cooled toroom temperature to provide the desired product.

Explosive Compositions:

The explosive compositions of the invention are water-in-oil emulsions.In one embodiment, these compositions are useful as bulk blastingcompositions or blasting agents. In another embodiment they are usefulas cap-sensitive explosives. These emulsions employ the inventiveemulsifier compositions as emulsifiers. These emulsions comprise adiscontinuous oxidizer phase comprising at least one oxygen-supplyingcomponent, a continuous organic phase comprising at least onecarbonaceous fuel, and an emulsifying amount of the inventiveemulsifier.

The organic phase of the explosive compositions of the invention ispreferably present at a level in the range of from about 2% to about 15%by weight, more preferably from about 4% to about 8% by weight based onthe total weight of said explosive composition. The inventive emulsifieris preferably present at a level in the range of from about 4% to about40% by weight, more preferably from about 12% to about 20% by weightbased on the total weight of the organic phase.

The oxidizer phase is preferably present at a level in the range of fromabout 85% to about 98% by weight, more preferably from about 92% toabout 96% by weight based on the total weight of said explosivecomposition. The oxygen-supplying component is preferably present at alevel in the range of from about 70% to about 95% by weight, morepreferably from about 85% to about 92% by weight, more preferably fromabout 87% to about 90% by weight based on the total weight of theoxidizer phase. The water is preferably present at a level in the rangeof about 5% to about 30% by weight, more preferably about 8% to about15% by weight, more preferably about 10% to about 13% by weight based onthe weight of the oxidizer phase.

The carbonaceous fuel can include most hydrocarbons, for example,paraffinic, olefinic, naphthenic, aromatic, saturated or unsaturatedhydrocarbons, and is typically in the form of an oil. In general, thecarbonaceous fuel is a water-immiscible, emulsifiable hydrocarbon thatis either liquid or liquefiable at temperatures of up to about 95° C.,and preferably between about 40° C. and about 75° C. Oils from a varietyof sources, including natural and synthetic oils and mixtures thereofcan be used as the carbonaceous fuel.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as solvent-refined or acid-refined mineral lubricatingoils of the paraffinic, naphthenic, or mixed paraffin-naphthenic types.Oils derived from coal or shale are also useful. Synthetic oils includehydrocarbon oils and halo-substituted hydrocarbon oils such aspolymerized and interpolymerized olefins (e.g., polybutylenes,polypropylenes, propylene-isobutylene copolymers, chlorinatedpolybutylenes, etc); alkyl benzenes (e.g., dodecylbenzenes,tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl) benzenes, etc.);polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.);and the like.

Another suitable class of synthetic oils that can be used comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid,fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols(e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexylalcohol, ethylene glycol, diethylene glycol monoether, propylene glycol,pentaerythritol, etc.). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)-sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctylphthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, the complex ester formed by reacting one mole ofsebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylol propane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-Siloxane oils and silicate oils comprise another class ofuseful oils. These include tetraethyl-silicate, tetraisopropyl-silicate,tetra-(2-ethylhexyl)-silicate, tetra-(4-methylhexyl)-silicate,tetra(p-tert-butylphenyl)-silicate,hexyl-(4-methyl-2-pentoxy)-di-siloxane, poly(methyl)siloxanes,poly-(methylphenyl)-siloxanes, etc. Other useful synthetic oils includeliquid esters of phosphorus-containing acid (e.g., tricresyl phosphate,trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.),polymeric tetrahydrofurans, and the like.

Unrefined, refined and rerefined oils (and mixtures of each with eachother) of the type disclosed hereinabove can be used. Unrefined oils arethose obtained directly from a natural or synthetic source withoutfurther purification treatment. For example, a shale oil obtaineddirectly from a retorting operation, a petroleum oil obtained directlyfrom distillation or ester oil obtained directly from an esterificationprocess and used without further treatment would be an unrefined oil.Refined oils are similar to the unrefined oils except that they havebeen further treated in one or more purification steps to improve one ormore properties. Many such purification techniques are known to those ofskill in the art such as solvent extraction, distillation, acid or baseextraction, filtration, percolation, etc. Rerefined oils are obtained byprocesses similar to those used to obtain refined oils applied torefined oils which have been already used in service. Such rerefinedoils are also known as reclaimed or reprocessed oils and often areadditionally processed by techniques directed toward removal of spentadditives and oil breakdown products.

Examples of useful oils include a white mineral oil available from WitcoChemical Company under the trade designation KAYDOL; a white mineral oilavailable from Shell under the trade designation ONDINA; a mineral oilavailable from Pennzoil under the trade designation N-750-HT; 40N oilavailable from Sun; refined mineral oil available from Witco ChemicalCompany under the name KLEAROL OIL; and a mineral seal oil availablefrom Exxon under the name MENTOR 28.

The carbonaceous fuel can be any wax having melting point of at leastabout 25° C., such as petrolatum wax, microcrystalline wax, and paraffinwax, mineral waxes such as ozocerite and montan wax, animal waxes suchas spermacetic wax, and insect waxes such as beeswax and Chinese wax.Useful waxes include waxes identified by the trade designation MOBILWAX57 which is available from Mobil Oil Corporation; D02764 which is ablended wax available from Astor Chemical Ltd.; and VYBAR which isavailable from Petrolite Corporation. Preferred waxes are blends ofmicrocrystalline waxes and paraffin.

In one embodiment, the carbonaceous fuel includes a combination of a waxand an oil. In this embodiment, the wax content is at least about 25%and preferably ranges from about 25% to about 90% by weight of theorganic phase, and the oil content is at least about 10% and preferablyranges from about 10% to about 75% by weight of the organic phase. Thesemixtures are particularly suitable for use in cap-sensitive explosiveemulsions.

While its presence is not necessary, the explosive emulsions can alsocontain up to about 15% by weight of an auxiliary fuel, such asaluminum, aluminum alloys, magnesium, and the like. Particulate aluminumis a preferred auxiliary fuel.

The oxygen-supplying component is preferably at least one inorganicoxidizer salt such as ammonium, alkali or alkaline earth metal nitrate,chlorate or perchlorate. Examples include ammonium nitrate, sodiumnitrate, calcium nitrate, ammonium chlorate, sodium perchlorate andammonium perchlorate. Ammonium nitrate is especially preferred. Mixturesof ammonium nitrate and sodium or calcium nitrate are also preferred. Inone embodiment, inorganic oxidizer salt comprises principally ammoniumnitrate, although up to about 25% by weight of the oxidizer phase cancomprise either another inorganic nitrate (e.g., alkali or alkalineearth metal nitrate) or an inorganic perchlorate (e.g., ammoniumperchlorate or an alkali or alkaline earth metal perchlorate) or amixture thereof.

In one embodiment of the invention, closed-cell, void-containingmaterials are used as sensitizing components. The term "closed-cell,void-containing material" is used herein to mean any particulatematerial which comprises closed cell, hollow cavities Each particle ofthe material can contain one or more closed cells, and the cells cancontain a gas, such as air, or can be evacuated or partially evacuated.In one embodiment of the invention, sufficient closed cell voidcontaining material is used to yield a density in the resulting emulsionof from about 0.8 to about 1.35 g/cc, more preferably about 0.9 to about1.3 g/cc, more preferably about 1.1 to about 1.3 g/cc. In general, theemulsions of the subject invention can contain up to about 15% byweight, preferably from about 0.25% to about 15% by weight of the closedcell void containing material. Preferred closed cell void containingmaterials are discrete glass spheres having a particle size within therange of about 10 to about 175 microns. In general, the bulk density ofsuch particles can be within the range of about 0.1 to about 0.4 g/cc.Useful glass microbubbles which can be used are the microbubbles sold by3M Company and which have a particle size distribution in the range offrom about 10 to about 160 microns and a nominal size in the range ofabout 60 to 70 microns, and densities in the range of from about 0.1 toabout 0.4 g/cc.; these include microbubbles distributed under the tradedesignation B15/250. Other useful glass microbubbles are sold under thetrade designation of ECCOSPHERES by Emerson & Cumming, Inc., andgenerally have a particle size range from about 44 to about 175 micronsand a bulk density of about 0.15 to about 0.4 g/cc. Other suitablemicrobubbles include the inorganic microspheres sold under the tradedesignation of Q-CEL by Philadelphia Quartz Company. The closed cellvoid containing material can be made of inert or reducing materials. Forexample, phenol-formaldehyde microbubbles can be utilized within thescope of this invention. If the phenol-formaldehyde microbubbles areutilized, the microbubbles themselves are a fuel component for theexplosive and their fuel value should be taken into consideration whendesigning a water-in-oil emulsion explosive composition. Another closedcell void containing material which can be used within the scope of thesubject invention is the saran microspheres sold by Dow ChemicalCompany. The saran microspheres have a diameter of about 30 microns anda particle density of about 0.032 g/cc. Because of the low bulk densityof the saran microspheres, it is preferred that only from about 0.25 toabout 1% by weight thereof be used in the water-in-oil emulsions of thesubject invention.

Gas bubbles which are generated in-situ by adding to the composition anddistributing therein a gas-generating material such as, for example, anaqueous solution of sodium nitrite and urea, can also be used can beused to sensitize the explosive emulsions. Other suitable sensitizingcomponents which may be employed alone or in addition to the foregoinginclude insoluble particulate solid self-explosives such as, forexample, grained or flaked TNT, DNT, RDX and the like and water-solubleand/or hydrocarbon-soluble organic sensitizers such as, for example,amine nitrates, alkanolamine nitrates, hydroxyalkyl nitrates, and thelike. The explosive emulsions of the present invention may be formulatedfor a wide range of applications. Any combination of sensitizingcomponents may be selected in order to provide an explosive compositionof virtually any desired density, weight-strength or critical diameter.The quantity of solid self-explosive ingredients and of water-solubleand/or hydrocarbon-soluble organic sensitizers may comprise up to about40% by weight of the total explosive composition. The volume of theoccluded gas component may comprise up to about 50% of the volume of thetotal explosive composition.

Optional additional materials may be incorporated in the explosivecompositions of the invention in order to further improve sensitivity,density, strength, rheology and cost of the final explosive. Typical ofmaterials found useful as optional additives include, for example,highly chlorinated paraffinic hydrocarbons, particulate oxygen-supplyingsalts such as prilled ammonium nitrate, calcium nitrate, perchlorates,and the like, particulate metal fuels such as aluminum, silicon and .thelike, particulate non-metal fuels such as sulfur, gilsonite and thelike, particulate inert materials such as sodium chloride, bariumsulphate and the like, water phase or hydrocarbon phase thickeners suchas guar gum, polyacrylamide, carboxymethyl or ethyl cellulose,biopolymers, starches, elastomeric materials, and the like, crosslinkersfor the thickeners such as potassium pyroantimonate and the like,buffers or pH controllers such as sodium borate, zinc nitrate and thelike, crystals habit modifiers such as alkyl naphthalene sodiumsulphonate and the like, liquid phase extenders such as formamide,ethylene glycol and the like and bulking agents and additives of commonuse in the explosives art. The quantities of optional additionalmaterials used may comprise up to about 50% by weight of the totalexplosive composition, the actual quantities employed depending upontheir nature and function.

The general criteria for cap-sensitivity is that the explosive besensitive to a No. 8 blasting cap at a cartridge diameter of 1.25 inchunder normal temperature conditions. The cap-sensitive explosiveemulsions of the present invention are shelf stable, which means theyexhibit shelf stability of at least six months and typically one year ormore.

A preferred method for making the explosive emulsions of the inventioncomprises the steps of (1) mixing water, inorganic oxidizer salts (e.g.,ammonium nitrate) and, in certain cases, some of the supplementalwater-soluble compounds, in a first premix, (2) mixing the carbonaceousfuel, the emulsifying salt compositions of the invention and any otheroptional oil-soluble compounds, in a second premix and (3) adding thefirst premix to the second premix in a suitable mixing apparatus, toform a water-in-oil emulsion. The first premix is heated until all thesalts are completely dissolved and the solution may be filtered ifneeded in order to remove any insoluble residue. The second premix isalso heated to liquefy the ingredients. Any type of apparatus capable ofeither low or high shear mixing can be used to prepare thesewater-in-oil emulsions. Closed-cell void containing materials,gas-generating materials, solid self-explosive ingredients such asparticulate TNT, solid fuels such as aluminum or sulfur, inert materialssuch as barytes or sodium chloride, undissolved solid oxidizer salts andother optional materials, if employed, are added to the emulsion andsimply blended until homogeneously dispersed throughout the composition.

The water-in-oil explosive emulsions of the invention can also beprepared by adding the second premix liquefied organic solution phase tothe first premix hot aqueous solution phase with sufficient stirring toinvert the phases. However, this method usually requires substantiallymore energy to obtain the desired dispersion than does the preferredreverse procedure. Alternatively, these water-in-oil explosive emulsionsare particularly adaptable to preparation by a continuous mixing processwhere the two separately prepared liquid phases are pumped through amixing device wherein they are combined and emulsified.

The emulsifier compositions of this invention can be added directly tothe inventive explosive emulsions. They can also be diluted with asubstantially inert, normally liquid organic diluent such as mineraloil, naphtha, benzene, toluene or xylene, to form a concentrate. In oneembodiment, the diluent is also useful as the carbonaceous fuel formaking the explosive emulsions. These concentrates usually contain fromabout 10% to about 90% by weight of the emulsifier composition of thisinvention and may contain, in addition, one or more other additivesknown in the art or described hereinabove.

Explosive cartridges within the scope of this invention can be madeusing techniques well known in the art. The cap-sensitive explosiveemulsions of the invention are particularly suitable for makingcartridges on cartridging machines such as the type available fromNiepmann under the trade designation ROLLEX.

An advantage of using the inventive emulsifier compositions is that saidcompositions impart anti-wear characteristics to the emulsions thusfacilitating processing and blending of said emulsions and reducing wearon the apparatus (e.g., mixers, pumps, etc.) used in preparing suchemulsions.

Illustrative emulsions within the scope of the invention are disclosedin the following Table. With each formulation, the oxidizer phasecomponents (i.e., ammonium nitrate and water) are mixed together atabout 130° C. The oil phase components (i.e., emulsifier compositionsfrom Examples 20-32 and 40N oil) are also mixed together at about 130°C. The oxidizer phase is added to the oil phase using a laboratory mixerto effect emulsification. The mixer is set at 70% of maximum powerduring emulsification and at full power for about one minute afteremulsification is completed. In the following table, all numericalvalues are in parts by weight.

                  TABLE                                                           ______________________________________                                                    A      B      C    D    E    F    G                               ______________________________________                                        Ammonium Nitrate                                                                          763.6  763.6  763.6                                                                              763.6                                                                              763.6                                                                              763.6                                                                              763.6                           Water       156.4  156.4  156.4                                                                              156.4                                                                              156.4                                                                              156.4                                                                              156.4                           40 N Oil     65.0   65.0   65.0                                                                               65.0                                                                               65.0                                                                               65.0                                                                               65.0                           Product of Ex. 20                                                                          15.0  --     --   --   --   --   --                              Product of Ex. 21                                                                         --      15.0  --   --   --   --   --                              Product of Ex. 22                                                                         --     --      15.0                                                                              --   --   --   --                              Product of Ex. 23                                                                         --     --     --    15.0                                                                              --   --   --                              Product of Ex. 24                                                                         --     --     --   --    15.0                                                                              --   --                              Product of Ex. 25                                                                         --     --     --   --   --    15.0                                                                              --                              Product of Ex. 26                                                                         --     --     --   --   --   --    15.0                           ______________________________________                                                    H      I      J    K    L    M                                    ______________________________________                                        Ammonium Nitrate                                                                          763.6  763.6  763.6                                                                              763.6                                                                              763.6                                                                              763.6                                Water       156.4  156.4  156.4                                                                              156.4                                                                              156.4                                                                              156.4                                40 N Oil     65.0   65.0   70.0                                                                               70.0                                                                               70.0                                                                               70.0                                Product of Ex. 27                                                                          15.0  --     --   --   --   --                                   Product of Ex. 28                                                                         --      15.0  --   --   --   --                                   Product of Ex. 29                                                                         --     --      10.0                                                                              --   --   --                                   Product of Ex. 30                                                                         --     --     --    10.0                                                                              --   --                                   Product of Ex. 31                                                                         --     --     --   --    10.0                                                                              --                                   Product of Ex. 32                                                                         --     --     --   --   --    10.0                                ______________________________________                                    

Glass microballoons can be added to each of the above indicatedemulsions by blending said microballoons into said emulsions with thelaboratory mixer. For example, water-in-oil emulsion eplosivecompositions containing 98.5-99.0% by weight of said emulsions and1.0-1.5% by weight of C15/250 glass microballoons can be made. Emulsionexplosive compositions can be made that contain by weight of the aboveemulsions and 3% by weight of B37/2000 glass microballoons.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

We claim:
 1. An explosive emulsion comprising a discontinuous oxidizerphase comprising at least one oxygen-supplying component, a continuousorganic phase comprising at least one carbonaceous fuel, and anemulsifying amount of a composition comprising the reaction product ofcomponent (I) with component (II);component (I) comprising: (A) thereaction product of(A)(i) at least one carboxylic acid or anhydride, orester or amide derived from said acid or anhydride, with (A)(ii)ammonia, at least one amine, at least one alkali metal and/or at leastone alkaline-earth metal; or (B) a composition comprising(B)(i) thereaction product of (B)(i)(a) at least one high-molecular weighthydrocarbyl-substituted carboxylic acid or anhydride, or ester or amidederived form said high-molecular weight acid or anhydride, with(B)(i)(b) ammonia, at least one amine, at least one alkali metal and/orat least one alkaline-earth metal, component (B)(i)(a) having at leastone hydrocarbyl substituent having an average of about 20 to about 500carbon atoms; and (B)(ii) the reaction product of (B)(ii)(a) at leastone low-molecular weight carboxylic acid or anhydride, or ester or amidederived from said low-molecular weight acid or anhydride, with(B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/orat least one alkaline-earth metal, component (B)(ii)(a) optionallyhaving at least one hydrocarbyl substituent having an average of up toabout 18 carbon atoms; or (C) a composition comprising(C)(i) thereaction product of (C)(i)(a) at least one high-molecular weighthydrocarbyl-substituted polycarboxylic acid or anhydride, or ester oramide derived from said high-molecular weight polycarboxylic acid oranhydride, with (C)(i)(b) ammonia, at least one amine, at least onealkali metal and/or at least one alkaline-earth metal, component(C)(i)(a) having at least one hydrocarbyl substituent having an averageof about 20 to about 500 carbon atoms; and (C)(ii) the reaction productof (C)(ii) (a) at least one low-molecular weight polycarboxylic acid oranhydride, or ester or amide derived from said low-molecular weightpolycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least oneamine, at least one alkali metal and/or at least one alkaline-earthmetal, component (C)(ii)(a) optionally having at least one hydrocarbylsubstituent having an average of up to about 18 carbon atoms; saidcomponents (C)(i) and (C)(ii) being couples together by (C)(iii) atleast one compound having (C)(iii)(a) two or more primary amino groups,(C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least oneprimary amino group and at least one secondary amino group, (C)(iii)(d)at least two hydroxyl groups, or (C)(iii)(e) at least one primary orsecondary amino group and at least one hydroxyl group; or (D) mixture oftwo or more of (A), (B) and (C); component (II) comprising: (A') atleast one phosphorous-containing acid represented by the formula##STR34## wherein X¹, X², X³ and X⁴ are independently oxygen or sulfur;a and b are independently zero or one, and R¹ and R² are independentlyhydrocarbyl groups; or (B') at least one salt derived from saidphosphorous-containing acid (A') and at least one metal selected fromthe group consisting of magnesium, calcium, strontium, chromium,manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc,cadmium, aluminum, tin, lead, and mixtures of two or more thereof; or(C') mixture of (A') and (B'); with the proviso that when component (II)is (A'), component (I) is (B), (C) or a mixture of (B) and (C).
 2. Anexplosive emulsion made by combining an oxidizer phase comprising atleast one oxygen-supplying component with an organic phase comprising atleast one carbonaceous fuel and a composition comprising the reactionproduct of component (1) with component (II);component (I) comprising:(A) the reaction product of(A)(i) at least one carboxylic acid oranhydride, or ester or amide derived from said acid or anhydride, with(A)(ii) ammonia, at least one amine, at least one alkali metal and/or atleast one alkaline-earth metal; or (B) a composition comprising(B)(i)the reaction product of (B)(i)(a) at least one high-molecular weighthydrocarbyl-substituted carboxylic acid or anhydride, or ester or amidederived from said high-molecular weight acid or anhydride, with(B)(i)(b) ammonia, at least one amine, at least one alkali metal and/orat least one alkaline-earth metal, component (B)(i)(a) having at leastone hydrocarbyl substituent having an average of about 20 to about 500carbon atoms; and (B)(ii) the reaction product of (B)(ii)(a) at leastone low-molecular weight carboxylic acid or anhydride, or ester or amidederived form said low-molecular weight acid or anhydride, with(B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/orat least one alkaline-earth metal, component (B)(ii)(a) optionallyhaving at least one hydrocarbyl substituent having an average of up toabout 18 carbon atoms; or (C) a composition comprising(C)(i) thereaction product of (C)(i)(a) at least one high-molecular weighthydrocarbyl-substituted polycarboxylic acid or anhydride, or ester oramide derived form said high-molecular weight polycarboxylic acid oranhydride, with (C)(i)(b) ammonia, at least one amine, at least onealkali metal and/or at least one alkaline-earth metal, component(C)(i)(a) having at least one hydrocarbyl substituent having an averageof about 20 to about 500 carbon atoms; and (C)(ii) the reaction productof (C)(ii)(a) at least one low-molecular weight polycarboxylic acid oranhydride, or ester or amide derived from said low-molecular weightpolycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least oneamine, at least one alkali metal and/or at least one alkaline-earthmetal, component (C)(ii)(a) optionally having at least one hydrocarbylsubstituent having an average of up to about 18 carbon atoms; saidcomponents (C)(i) and (C)(ii) being coupled together by (C)(iii) atleast one compound having (C)(iii)(a) two or more primary amino groups,(C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least oneprimary amino group and at least one secondary amino group, (C)(iii)(d)at least two hydroxyl groups, or (C)(iii)(e) at least one primary orsecondary amino group and at least one hydroxyl group; or (D) mixture oftwo or mote of (A), (B) and (C); component (II) comprising: (A') atleast one phosphorous-containing acid represented by the formula##STR35## wherein X¹, X², X³ and X⁴ are independently oxygen or sulfur;a and b are independently zero or one, and R¹ and R² are independentlyhydrocarbyl groups; or (B') at least one salt derived from saidphosphorous-containing acid (A') and at least one metal selected fromthe group consisting of magnesium, calcium, strontium, chromium,manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc,cadmium, aluminum, tin, lead, and mixtures of two or more thereof; or(C') mixture of (A') and (B'); with the proviso that when component (II)is (A'), component (I) is (B), (C) or a mixture of (B) and (C).
 3. Acap-sensitive explosive emulsion comprising a discontinuous oxidizerphase comprising at least one oxygen-supplying component, a continuousorganic phase comprising at least one carbonaceous fuel, saidcarbonaceous fuel comprising at least one wax, and an emulsifying amountof a composition comprising the reaction product of component (I) withcomponent (II);component (I) comprising: (A) the reaction productof(A)(i) at least one carboxylic acid or anhydride, or ester or amidederived from said acid or anhydride, with (A)(ii) ammonia, at least oneamine, at least one alkali metal and/or at least one alkaline-earthmetal; or (B) a composition comprising(B)(i) the reaction product of(B)(i)(a) at least one high-molecular weight hydrocarbyl-substitutedcarboxylic acid or anhydride, or ester or amide derived form saidhigh-molecular weight acid or anhydride, with (B)(i)(b) ammonia, atleast one amine, at least one alkali metal and/or at least onealkaline-earth metal, component (B)(i)(a) having at least onehydrocarbyl substituent having an average of about 20 to about 500carbon atoms; and (B)(ii) the reaction product of (B)(ii)(a) at leastone low-molecular weight carboxylic acid or anhydride, or ester or amidederived from said low-molecular weight acid or anhydride, with(B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/orat least one alkaline-earth metal, component (B)(ii)(a) optionallyhaving at least one hydrocarbyl substituent having an average of up toabout 18 carbon atoms; or (C) a composition comprising(C)(i) thereaction product of (C)(i)(a) at least one high-molecular weighthydrocarbyl-substituted polycarboxylic acid or anhydride, or ester oramide derived from said high-molecular weight polycarboxylic acid oranhydride, with (C)(i)(b) ammonia, at least one amine, at least onealkali metal and/or at least one alkaline-earth metal component(C)(i)(a) having at least one hydrocarbyl substituent having an averageof about 20 to about 500 carbon atoms; and (C)(ii) the reaction productof (C)(ii)(a) at least one low-molecular weight polycarboxylic acid oranhydride, or ester or amide derived from said low-molecular weightpolycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least oneamine, at least one alkali metal and/or at least one alkaline-earthmetal, component (C)(ii)(a) optionally having at least one hydrocarbylsubstituent having an average of up to about 18 carbon atoms; saidcomponents (C)(i) and (C)(ii) being coupled together by (C)(iii) atleast one compound having (C)(iii)(a) two or more primary amino groups,(C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least oneprimary amino group and at least one secondary amino group, (C)(iii)(d)at least two hydroxyl groups, or (C)(iii)(e) at least one primary orsecondary amino group and at least one hydroxyl group; or (D) mixture oftwo or more of (A), (B) and (C); component (II) comprising: (A') atleast one phosphorus-containing acid represented by the formula##STR36## wherein X¹, X², X³ and X⁴ are independently oxygen or sulfur;a and b are independently zero or one, and R¹ and R² are independentlyhydrocarbyl groups; or (B') at least one salt derived from saidphosphorous-containing acid (A') and at least one metal selected fromthe group consisting of magnesium, calcium, strontium, chromium,manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc,cadmium, aluminum, tin, lead, and mixtures of two or more thereof; or(C') mixture of (A') and (B'); with the proviso that when component (II)is (A'), component (I) is (B), (C) or a mixture of (B) and (C).
 4. Acartridge comprising a cartridge shell containing a cap-sensitiveexplosive emulsion; said emulsion comprising a discontinuous oxidizerphase comprising at least one oxygen-supplying component, a continuousorganic phase comprising at least one carbonaceous duel, saidcarbonaceous fuel comprising at least one wax, and an emulsifying amountof a composition comprising the reaction product of component (I) withcomponent (II);component (I) comprising: (A) the reaction productof(A)(i) at least one carboxylic acid or anhydride, or ester or amidederived from said acid or anhydride, with (A)(ii) ammonia, at least oneamine, at least one alkali metal and/or at least one alkaline-earthmetal; or (B) a composition comprising(B)(i) the reaction product of(B)(i)(a) at least one high-molecular weight hydrocarbyl-substitutedcarboxylic acid or anhydride, or ester or amide derived from saidhigh-molecular weight acid or anhydride, with (B)(i)(b) ammonia, atleast one amine, at least one alkali metal and/or at least onealkaline-earth metal, component (B)(i)(a) having at least onehydrocarbyl substituent having an average of about 20 to about 500carbon atoms; and (B)(ii) the reaction product of (B)(ii)(a) at leastone low-molecular weight carboxylic acid or anhydride, or ester or amidederived from said low-molecular weight acid or anhydride, with(B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/orat least one alkaline-earth metal, component (B)(ii)(a) optionallyhaving at least one hydrocarbyl substituent having an average of up toabout 18 carbon atoms; or (C) a composition comprising(C)(i) thereaction product of (C)(i)(a) at least one high-molecular weighthydrocarbyl-substituted polycarboxylic acid or anhydride, or ester oramide derived from s aid high-molecular weight polycarboxylic acid oranhydride, with (C)(i)(b) ammonia, at least one amine, at least onealkali metal and/or at least one alkaline-earth metal, component(C)(i)(a) having at least one hydrocarbyl substituent having an averageof about 20 to 500 carbon atoms; and (C)(ii) the reaction product of(C)(ii)(a) at least one low-molecular weight polycarboxylic acid oranhydride, or ester or amide derived from said low-molecualar weightpolycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least oneamine, at least one alkaIi metal and/or at least one alkaline-earthmetal, component (C)(ii)(a) optionally having at least one hydrocarbylsubstituent having an average of up to about 18 carbon atoms; saidcomponents (C)(i) and (C)(ii) being coupled together by (C)(iii) atleast one compound having (C)(iii)(a) two or more primary amino groups,(C)(iii)(c) at least one primary amino group and at least one secondaryamino group, (C)(iii)(d) at least two hydroxyl groups, or (C)(iii)(e) atleast one primary or secondary amino group and at least one hydroxylgroup; or (D) mixture of two or more of (A), (B) and (C); component (II)comprising: (A') at least one phosphorus-containing acid represented bythe formula ##STR37## wherein X¹, X², X³ and X⁴ are independently oxygenor sulfur; a and b are independently zero or one, and R¹ and R² areindependently hydrocarbyl groups; or (B') at least one salt derived fromsaid phosphorous-containing acid (A') and at least one metal selectedfrom the group consisting of magnesium, calcium, strontium, chromium,manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc,cadmium, aluminum, tin, lead, and mixtures or two or more thereof; or(C') mixture of (A') and (B'); with the proviso that when component (II)is (A'), component (I) is (B), (C) or a mixture of (B) and (C).
 5. Acartridge having a diameter of about 1.25 inches or less comprising atleast one cap-sensitive explosive emulsion; said emulsion comprising adiscontinuous oxidizer phase comprising at least one oxygen-supplyingcomponent, a continuous organic phase comprising at least onecarbonaceous fuel, and an emulsifying amount of a composition comprisingthe reaction product of component (I) with component (II);component (I)comprising: (A) the reaction product of(A)(i) at least one carboxylicacid or anhydride, or ester or amide derived from said acid oranhydride, with (A)(ii) ammonia, at least one amine, at least one alkalimetal and/or at least one alkaline-earth metal; or (B) a compositioncomprising(B)(i) the reaction product of (B)(i)(a) at least onehigh-molecular weight hydrocarbyl-substituted carboxylic acid oranhydride, or ester or amide derived from said high-molecular weightacid or anhydride, with (B)(i)(b) ammonia, at least one amine, at leastone alkali metal and/or at least one alkaline-earth metal, component(B)(i)(a) having at least one hydrocarbyl substituent having an averageof about 20 to about 500 carbon atoms; and (B)(ii) the reaction productof (B)(ii)(a) at least one low-molecular weight carboxylic acid oranhydride, or ester or amide derived form said low-molecular weight acidor anhydride, with (B)(ii)(b) ammonia, at least one amine, at least onealkali metal and/or at least one alkaline-earth metal, component(B)(ii)(a) optionally having at least one hydrocarbyl substituent havingan average of up to about 18 carbon atoms; or (C) a compositioncomprising(C)(i) the reaction product of (C)(i)(a) at least onehigh-molecular weight hydrocarbyl-substituted polycarboxylic acid oranhydride, or ester or amide derived from said high-molecular weightpolycarboxylic acid or anhydride, with (C)(i)(b) ammonia, at least oneamine, at least one alkali metal and/or at least one alkaline-earthmetal, component (C)(i)(a) having at least one hydrocarbyl substituenthaving an average of about 20 to about 500 carbon atoms; and (C)(ii) thereaction product of (C)(ii)(a) at least one low-molecular weightpolycarboxylic acid or anhydride, or ester or amide derived from saidlow-molecular weight polycarboxylic acid or anhydride, with (C)(ii)(b)ammonia, at least one amine, at least one alkali metal and/or at leastone alkaline-earth metal, component (C)(ii)(a) optionally having atleast one hydrocarbyl substituent having an average of up to about 18carbon atoms; said components (C)(i) and (C)(ii) being coupled togetherby (C)(iii) at least one compound having (C)(iii)(a) two or more primaryamino groups, (C)(iii)(b) two or more secondary amino groups,(C)(iii)(c) at least one primary group and at least one secondary aminogroup, (C)(iii)(d) at least two hydroxyl groups, or (C)(iii)(e) at leastone primary or secondary amino group and at least one hydroxyl group; or(D) mixture of two or more of (A), (B) and (C); component (II)comprising: (A') at least one phosphorus-containing acid represented bythe formula ##STR38## wherein X¹, X², X³ and X⁴ are independently oxygenor sulfur; a and b are independently zero or one, and R¹ and R² areindependently hydrocarbyl groups; or (B') at least one salt derived fromsaid phosphorous-containing acid (A') and at least one metal selectedfrom the group consisting of magnesium, calcium, strontium, chromium,manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc,cadmium, aluminum, tin, lead, and mixtures of two or, more thereof; or(C') mixture or (A') and (B'); with the proviso that when component (II)is (A'), component (1) is (B), (C) or a mixture of (B) and (C).